# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1491233'
_audit_update_record             
;
2016-07-07 deposited with the CCDC.
2016-09-01 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C144 H72 Cl3 Hf12 Ir3 N12 O64'
_chemical_formula_weight         5818.96

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Hf Hf -6.1794 4.9776 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ir Ir -4.7710 6.5667 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           229
_space_group_name_H-M_alt        'I m -3 m'
_space_group_name_Hall           '-I 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'
'-y, x, z'
'-x, -y, z'
'y, -x, z'
'x, -z, y'
'x, -y, -z'
'x, z, -y'
'z, y, -x'
'-x, y, -z'
'-z, y, x'
'z, x, y'
'y, z, x'
'-y, -z, x'
'z, -x, -y'
'-y, z, -x'
'-z, -x, y'
'-z, x, -y'
'y, -z, -x'
'y, x, -z'
'-y, -x, -z'
'-x, z, y'
'-x, -z, -y'
'z, -y, x'
'-z, -y, -x'
'x+1/2, y+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'y+1/2, -x+1/2, z+1/2'
'x+1/2, -z+1/2, y+1/2'
'x+1/2, -y+1/2, -z+1/2'
'x+1/2, z+1/2, -y+1/2'
'z+1/2, y+1/2, -x+1/2'
'-x+1/2, y+1/2, -z+1/2'
'-z+1/2, y+1/2, x+1/2'
'z+1/2, x+1/2, y+1/2'
'y+1/2, z+1/2, x+1/2'
'-y+1/2, -z+1/2, x+1/2'
'z+1/2, -x+1/2, -y+1/2'
'-y+1/2, z+1/2, -x+1/2'
'-z+1/2, -x+1/2, y+1/2'
'-z+1/2, x+1/2, -y+1/2'
'y+1/2, -z+1/2, -x+1/2'
'y+1/2, x+1/2, -z+1/2'
'-y+1/2, -x+1/2, -z+1/2'
'-x+1/2, z+1/2, y+1/2'
'-x+1/2, -z+1/2, -y+1/2'
'z+1/2, -y+1/2, x+1/2'
'-z+1/2, -y+1/2, -x+1/2'
'-x, -y, -z'
'y, -x, -z'
'x, y, -z'
'-y, x, -z'
'-x, z, -y'
'-x, y, z'
'-x, -z, y'
'-z, -y, x'
'x, -y, z'
'z, -y, -x'
'-z, -x, -y'
'-y, -z, -x'
'y, z, -x'
'-z, x, y'
'y, -z, x'
'z, x, -y'
'z, -x, y'
'-y, z, x'
'-y, -x, z'
'y, x, z'
'x, -z, -y'
'x, z, y'
'-z, y, -x'
'z, y, x'
'-x+1/2, -y+1/2, -z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'x+1/2, y+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'-x+1/2, z+1/2, -y+1/2'
'-x+1/2, y+1/2, z+1/2'
'-x+1/2, -z+1/2, y+1/2'
'-z+1/2, -y+1/2, x+1/2'
'x+1/2, -y+1/2, z+1/2'
'z+1/2, -y+1/2, -x+1/2'
'-z+1/2, -x+1/2, -y+1/2'
'-y+1/2, -z+1/2, -x+1/2'
'y+1/2, z+1/2, -x+1/2'
'-z+1/2, x+1/2, y+1/2'
'y+1/2, -z+1/2, x+1/2'
'z+1/2, x+1/2, -y+1/2'
'z+1/2, -x+1/2, y+1/2'
'-y+1/2, z+1/2, x+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, x+1/2, z+1/2'
'x+1/2, -z+1/2, -y+1/2'
'x+1/2, z+1/2, y+1/2'
'-z+1/2, y+1/2, -x+1/2'
'z+1/2, y+1/2, x+1/2'

_cell_length_a                   38.3207(2)
_cell_length_b                   38.3207(2)
_cell_length_c                   38.32070(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     56273.0(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    11933
_cell_measurement_theta_min      3.4310
_cell_measurement_theta_max      64.7640

_exptl_crystal_description       Block
_exptl_crystal_colour            Red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.687
_exptl_crystal_F_000             10712
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    5.633
_shelx_estimated_absorpt_T_min   0.603
_shelx_estimated_absorpt_T_max   0.603
_exptl_absorpt_correction_T_min  0.58601
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            18019
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_av_R_equivalents  0.0398
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         3.647
_diffrn_reflns_theta_max         64.772
_diffrn_reflns_theta_full        64.772
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measured_fraction_theta_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_point_group_measured_fraction_full 0.977
_reflns_number_total             4361
_reflns_number_gt                4146
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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.
;

_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0912P)²+1988.9337P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4361
_refine_ls_number_parameters     102
_refine_ls_number_restraints     97
_refine_ls_R_factor_all          0.1011
_refine_ls_R_factor_gt           0.0991
_refine_ls_wR_factor_ref         0.2476
_refine_ls_wR_factor_gt          0.2464
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_restrained_S_all      1.099
_refine_ls_shift/su_max          0.001
_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 0.27144(2) 0.20721(2) 0.20721(2) 0.0803(4) Uani 1 2 d DS T P . .
Ir1 Ir 0.5000 0.2500 0.0000 0.1274(11) Uani 1 8 d S TU P . .
Cl1 Cl 0.5000 0.3143(11) 0.0000 0.28(2) Uani 0.5 4 d S TU P . .
O1 O 0.3155(2) 0.2224(3) 0.1721(2) 0.086(3) Uani 1 1 d D U . . .
O2 O 0.3056(4) 0.2422(3) 0.2422(3) 0.109(5) Uani 1 2 d DS TU P . .
O3 O 0.2496(3) 0.1957(5) 0.1528(3) 0.170(6) Uani 1 1 d D U . . .
O4 O 0.2144(3) 0.2144(3) 0.2144(3) 0.061(4) Uani 1 6 d DS TU P . .
N1 N 0.5000 0.2479(3) 0.0522(2) 0.059(3) Uani 1 2 d S TU P . .
C1 C 0.4712(3) 0.2468(3) 0.0724(3) 0.069(3) Uani 1 1 d . U . . .
C2 C 0.4814(3) 0.2443(4) 0.1087(3) 0.091(4) Uani 1 1 d . U . . .
H2 H 0.4665 0.2429 0.1284 0.109 Uiso 1 1 calc R U . . .
C3 C 0.4373(2) 0.2500 0.0627(2) 0.059(4) Uani 1 2 d S TU P . .
C4 C 0.4093(4) 0.2500 0.0907(4) 0.085(5) Uani 1 2 d S TU P . .
C5 C 0.4028(4) 0.2791(5) 0.1088(4) 0.107(5) Uani 1 1 d . U . . .
H5 H 0.4163 0.2994 0.1045 0.128 Uiso 1 1 calc R U . . .
C6 C 0.3764(4) 0.2798(4) 0.1339(4) 0.090(4) Uani 1 1 d . U . . .
H6 H 0.3709 0.3009 0.1457 0.108 Uiso 1 1 calc R U . . .
C7 C 0.3587(3) 0.2500 0.1413(3) 0.075(5) Uani 1 2 d S TU P . .
C8 C 0.3303(4) 0.2500 0.1697(4) 0.083(5) Uani 1 2 d S TU 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 O2 2.067(8) 84 ?
Hf1 O2 2.067(8) 83 ?
Hf1 O4 2.221(8) . ?
Hf1 O1 2.234(8) 70 ?
Hf1 O1 2.234(8) . ?
Hf1 O3 2.290(13) 70 ?
Hf1 O3 2.290(13) . ?
Hf1 O2 2.305(14) . ?
Hf1 Hf1 3.478(2) 83 ?
Hf1 Hf1 3.478(2) 84 ?
Hf1 Hf1 3.4810(11) 12 ?
Hf1 Hf1 3.4810(11) 11 ?
Ir1 N1 2.001(10) 82 ?
Ir1 N1 2.001(10) 80_554 ?
Ir1 N1 2.001(10) 51 ?
Ir1 N1 2.001(10) . ?
Ir1 Cl1 2.47(4) . ?
Ir1 Cl1 2.47(4) 80_554 ?
O1 C8 1.202(11) . ?
O2 Hf1 2.067(8) 83 ?
O2 Hf1 2.067(8) 84 ?
O4 Hf1 2.221(8) 12 ?
O4 Hf1 2.221(8) 11 ?
N1 C1 1.348(11) 54_655 ?
N1 C1 1.348(11) . ?
C1 C3 1.359(12) . ?
C1 C2 1.449(16) . ?
C2 C2 1.42(3) 54_655 ?
C2 H2 0.9500 . ?
C3 C1 1.359(12) 48 ?
C3 C4 1.52(2) . ?
C4 C5 1.333(18) . ?
C4 C5 1.333(18) 48 ?
C5 C6 1.399(18) . ?
C5 H5 0.9500 . ?
C6 C7 1.357(16) . ?
C6 H6 0.9500 . ?
C7 C6 1.357(16) 48 ?
C7 C8 1.54(2) . ?
C8 O1 1.202(11) 48 ?

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
O2 Hf1 O2 112.5(8) 84 83 ?
O2 Hf1 O4 70.4(4) 84 . ?
O2 Hf1 O4 70.4(4) 83 . ?
O2 Hf1 O1 144.8(4) 84 70 ?
O2 Hf1 O1 78.6(4) 83 70 ?
O4 Hf1 O1 141.8(3) . 70 ?
O2 Hf1 O1 78.6(4) 84 . ?
O2 Hf1 O1 144.8(4) 83 . ?
O4 Hf1 O1 141.8(3) . . ?
O1 Hf1 O1 75.2(5) 70 . ?
O2 Hf1 O3 135.7(5) 84 70 ?
O2 Hf1 O3 82.6(6) 83 70 ?
O4 Hf1 O3 77.1(5) . 70 ?
O1 Hf1 O3 77.2(4) 70 70 ?
O1 Hf1 O3 113.4(5) . 70 ?
O2 Hf1 O3 82.6(6) 84 . ?
O2 Hf1 O3 135.7(5) 83 . ?
O4 Hf1 O3 77.1(5) . . ?
O1 Hf1 O3 113.4(5) 70 . ?
O1 Hf1 O3 77.2(4) . . ?
O3 Hf1 O3 61.1(8) 70 . ?
O2 Hf1 O2 74.7(5) 84 . ?
O2 Hf1 O2 74.7(5) 83 . ?
O4 Hf1 O2 114.6(6) . . ?
O1 Hf1 O2 76.6(4) 70 . ?
O1 Hf1 O2 76.6(4) . . ?
O3 Hf1 O2 148.1(4) 70 . ?
O3 Hf1 O2 148.1(4) . . ?
O2 Hf1 Hf1 93.6(4) 84 83 ?
O2 Hf1 Hf1 39.8(4) 83 83 ?
O4 Hf1 Hf1 94.9(4) . 83 ?
O1 Hf1 Hf1 73.6(3) 70 83 ?
O1 Hf1 Hf1 109.2(3) . 83 ?
O3 Hf1 Hf1 118.8(4) 70 83 ?
O3 Hf1 Hf1 172.0(3) . 83 ?
O2 Hf1 Hf1 35.0(2) . 83 ?
O2 Hf1 Hf1 39.8(4) 84 84 ?
O2 Hf1 Hf1 93.6(4) 83 84 ?
O4 Hf1 Hf1 94.9(4) . 84 ?
O1 Hf1 Hf1 109.2(3) 70 84 ?
O1 Hf1 Hf1 73.6(3) . 84 ?
O3 Hf1 Hf1 172.0(3) 70 84 ?
O3 Hf1 Hf1 118.8(4) . 84 ?
O2 Hf1 Hf1 35.0(2) . 84 ?
Hf1 Hf1 Hf1 60.06(4) 83 84 ?
O2 Hf1 Hf1 89.4(4) 84 12 ?
O2 Hf1 Hf1 32.6(4) 83 12 ?
O4 Hf1 Hf1 38.4(3) . 12 ?
O1 Hf1 Hf1 110.4(2) 70 12 ?
O1 Hf1 Hf1 163.6(3) . 12 ?
O3 Hf1 Hf1 83.0(4) 70 12 ?
O3 Hf1 Hf1 112.7(3) . 12 ?
O2 Hf1 Hf1 89.5(3) . 12 ?
Hf1 Hf1 Hf1 59.97(2) 83 12 ?
Hf1 Hf1 Hf1 90.0 84 12 ?
O2 Hf1 Hf1 32.6(4) 84 11 ?
O2 Hf1 Hf1 89.4(4) 83 11 ?
O4 Hf1 Hf1 38.4(3) . 11 ?
O1 Hf1 Hf1 163.6(3) 70 11 ?
O1 Hf1 Hf1 110.4(2) . 11 ?
O3 Hf1 Hf1 112.7(3) 70 11 ?
O3 Hf1 Hf1 83.0(4) . 11 ?
O2 Hf1 Hf1 89.5(3) . 11 ?
Hf1 Hf1 Hf1 90.0 83 11 ?
Hf1 Hf1 Hf1 59.97(2) 84 11 ?
Hf1 Hf1 Hf1 60.0 12 11 ?
N1 Ir1 N1 175.5(8) 82 80_554 ?
N1 Ir1 N1 90.09(3) 82 51 ?
N1 Ir1 N1 90.09(3) 80_554 51 ?
N1 Ir1 N1 90.09(3) 82 . ?
N1 Ir1 N1 90.09(3) 80_554 . ?
N1 Ir1 N1 175.5(8) 51 . ?
N1 Ir1 Cl1 87.7(4) 82 . ?
N1 Ir1 Cl1 87.7(4) 80_554 . ?
N1 Ir1 Cl1 92.3(4) 51 . ?
N1 Ir1 Cl1 92.3(4) . . ?
N1 Ir1 Cl1 92.3(4) 82 80_554 ?
N1 Ir1 Cl1 92.3(4) 80_554 80_554 ?
N1 Ir1 Cl1 87.7(4) 51 80_554 ?
N1 Ir1 Cl1 87.7(4) . 80_554 ?
Cl1 Ir1 Cl1 180.0 . 80_554 ?
C8 O1 Hf1 129.1(11) . . ?
Hf1 O2 Hf1 114.7(7) 83 84 ?
Hf1 O2 Hf1 105.3(5) 83 . ?
Hf1 O2 Hf1 105.3(5) 84 . ?
Hf1 O4 Hf1 103.2(5) . 12 ?
Hf1 O4 Hf1 103.2(5) . 11 ?
Hf1 O4 Hf1 103.2(5) 12 11 ?
C1 N1 C1 109.7(11) 54_655 . ?
C1 N1 Ir1 125.2(6) 54_655 . ?
C1 N1 Ir1 125.2(6) . . ?
N1 C1 C3 128.5(10) . . ?
N1 C1 C2 109.5(9) . . ?
C3 C1 C2 121.8(10) . . ?
C2 C2 C1 105.6(6) 54_655 . ?
C2 C2 H2 127.2 54_655 . ?
C1 C2 H2 127.2 . . ?
C1 C3 C1 122.1(13) 48 . ?
C1 C3 C4 118.9(6) 48 . ?
C1 C3 C4 118.9(6) . . ?
C5 C4 C5 120(2) . 48 ?
C5 C4 C3 119.8(10) . . ?
C5 C4 C3 119.8(10) 48 . ?
C4 C5 C6 120.4(17) . . ?
C4 C5 H5 119.8 . . ?
C6 C5 H5 119.8 . . ?
C7 C6 C5 119.3(15) . . ?
C7 C6 H6 120.3 . . ?
C5 C6 H6 120.3 . . ?
C6 C7 C6 119.8(17) 48 . ?
C6 C7 C8 120.1(8) 48 . ?
C6 C7 C8 120.1(8) . . ?
O1 C8 O1 134(2) 48 . ?
O1 C8 C7 112.8(10) 48 . ?
O1 C8 C7 112.8(10) . . ?

_refine_diff_density_max         1.485
_refine_diff_density_min         -5.540
_refine_diff_density_rms         0.184



