# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2024

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_zrb4-2-273_b
_database_code_depnum_ccdc_archive 'CCDC 2173083'
loop_
_audit_author_name
_audit_author_address
'Horst Schmidt'
;TU Freiberg
Germany
;
_audit_update_record             
;
2022-05-16 deposited with the CCDC.	2024-01-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'B4 H16 Zr'
_chemical_formula_weight         150.59

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           215
_space_group_name_H-M_alt        'P -4 3 m'
_space_group_name_Hall           'P -4 2 3'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'

_cell_length_a                   5.955(11)
_cell_length_b                   5.955(11)
_cell_length_c                   5.955(11)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     211.1(12)
_cell_formula_units_Z            1
_cell_measurement_temperature    273
_cell_measurement_reflns_used    98
_cell_measurement_theta_min      3.35
_cell_measurement_theta_max      24.89

_exptl_crystal_description       cubic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.184
_exptl_crystal_F_000             76
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    1.187
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      273(2)
__diffrn_measurement_device      '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_type            STOE
_diffrn_detector_area_resol_mean 6.67
_diffrn_source                   
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_voltage           50
_diffrn_source_current           40
_diffrn_source_power             2.000
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_measurement_method       'rotation method'
_diffrn_measurement_details      
; 413 frames, detector distance = 100 mm
;
_diffrn_reflns_number            3767
_diffrn_reflns_av_unetI/netI     0.0276
_diffrn_reflns_av_R_equivalents  0.1331
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_theta_min         6.855
_diffrn_reflns_theta_max         27.285
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.959
_diffrn_measured_fraction_theta_full 0.952
_diffrn_reflns_Laue_measured_fraction_max 0.959
_diffrn_reflns_Laue_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_point_group_measured_fraction_full 0.959
_reflns_number_total             115
_reflns_number_gt                115
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.620
_reflns_Friedel_fraction_max     0.978
_reflns_Friedel_fraction_full    0.972

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_computing_data_collection       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     'w=1/[σ²(Fo²)] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.93(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.5(5)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         115
_refine_ls_number_parameters     12
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0114
_refine_ls_R_factor_gt           0.0114
_refine_ls_wR_factor_ref         0.0272
_refine_ls_wR_factor_gt          0.0272
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_restrained_S_all      1.052
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Zr1 Zr 0.500000 0.500000 0.500000 0.0628(3) Uani 1 24 d S T P . .
B1 B 0.7238(7) 0.2762(7) 0.2762(7) 0.0968(18) Uani 1 6 d S T P . .
H1 H 0.554(5) 0.253(4) 0.253(4) 0.075(9) Uiso 1 2 d S . P . .
H2 H 0.816(8) 0.184(8) 0.184(8) 0.11(2) Uiso 1 6 d S . P . .


_geom_special_details            
;
 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.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Zr1 B1 2.308(8) . ?
Zr1 B1 2.308(8) 4_566 ?
Zr1 B1 2.308(8) 2_665 ?
Zr1 B1 2.308(8) 3_656 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
B1 Zr1 B1 109.471(1) . 4_566 ?
B1 Zr1 B1 109.5 . 2_665 ?
B1 Zr1 B1 109.5 4_566 2_665 ?
B1 Zr1 B1 109.5 . 3_656 ?
B1 Zr1 B1 109.5 4_566 3_656 ?
B1 Zr1 B1 109.471(1) 2_665 3_656 ?

_refine_diff_density_max         0.086
_refine_diff_density_min         -0.075
_refine_diff_density_rms         0.017



####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_HfB4-3a
_database_code_depnum_ccdc_archive 'CCDC 2173084'
loop_
_audit_author_name
_audit_author_address
'Horst Schmidt'
;TU Freiberg
Germany
;
_audit_update_record             
;
2022-05-16 deposited with the CCDC.	2024-01-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'B4 H16 Hf'
_chemical_formula_weight         237.86

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Hf Hf -0.5830 6.1852 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           215
_space_group_name_H-M_alt        'P -4 3 m'
_space_group_name_Hall           'P -4 2 3'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'

_cell_length_a                   5.946(10)
_cell_length_b                   5.946(10)
_cell_length_c                   5.946(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     210.3(62)
_cell_formula_units_Z            1
_cell_measurement_temperature    288
_cell_measurement_reflns_used    120
_cell_measurement_theta_min      3.38
_cell_measurement_theta_max      27.17

_exptl_crystal_description       cube
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.903
_exptl_crystal_F_000             108
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    12.450
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   integration
_exptl_absorpt_correction_T_min  0.0234
_exptl_absorpt_correction_T_max  0.0605
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_measurement_device       '2-circle goniometer'
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_type            STOE
_diffrn_detector_area_resol_mean 6.67
_diffrn_source                   
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_voltage           50
_diffrn_source_current           40
_diffrn_source_power             2.000
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_ambient_temperature      288
_diffrn_measurement_method       'rotation method'
_diffrn_measurement_details      
; 213 frames, detector distance = 100 mm
;
_diffrn_reflns_number            2072
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_av_R_equivalents  0.0805
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         6.895
_diffrn_reflns_theta_max         29.668
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.955
_diffrn_measured_fraction_theta_full 0.933
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_Laue_measured_fraction_full 0.933
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_point_group_measured_fraction_full 0.936
_reflns_number_total             135
_reflns_number_gt                135
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.607
_reflns_Friedel_fraction_max     0.944
_reflns_Friedel_fraction_full    0.941

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_computing_data_collection       'STOE X-AREA'
_computing_cell_refinement       'STOE X-AREA'
_computing_data_reduction        'STOE X-RED'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0595P)²+0.5000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.17(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.4(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         135
_refine_ls_number_parameters     12
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0341
_refine_ls_wR_factor_ref         0.0951
_refine_ls_wR_factor_gt          0.0951
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_restrained_S_all      1.040
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Hf1 Hf 0.500000 0.500000 0.500000 0.0611(10) Uani 1 24 d S T P . .
B1 B 0.276(2) 0.276(2) 0.276(2) 0.054(5) Uani 1 6 d DS T P . .
H1 H 0.245(15) 0.474(5) 0.245(15) 0.04(3) Uiso 1 2 d DS . P . .
H2 H 0.159(2) 0.159(2) 0.159(2) 0.06(8) Uiso 1 6 d DS . P . .


_geom_special_details            
;
 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.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Hf1 B1 2.30(2) 2_665 ?
Hf1 B1 2.30(2) 4_566 ?
Hf1 B1 2.30(2) 3_656 ?
Hf1 B1 2.30(2) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
B1 Hf1 B1 109.471(2) 2_665 4_566 ?
B1 Hf1 B1 109.471(2) 2_665 3_656 ?
B1 Hf1 B1 109.5 4_566 3_656 ?
B1 Hf1 B1 109.471(1) 2_665 . ?
B1 Hf1 B1 109.471(2) 4_566 . ?
B1 Hf1 B1 109.471(1) 3_656 . ?

_refine_diff_density_max         0.910
_refine_diff_density_min         -0.781
_refine_diff_density_rms         0.249



