# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1043280'
_audit_update_record             
;
2015-01-13 deposited with the CCDC.
2015-03-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C216 H130 N12 O32 Zr6'
_chemical_formula_weight         3952.63

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'
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'
Zr Zr -0.1862 2.2449 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_H-M_alt        'P m -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'
'-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, -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'

_cell_length_a                   25.43760(10)
_cell_length_b                   25.43760(10)
_cell_length_c                   25.43760(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     16459.95(19)
_cell_formula_units_Z            1
_cell_measurement_temperature    293.00(10)
_cell_measurement_reflns_used    12119
_cell_measurement_theta_min      3.8720
_cell_measurement_theta_max      73.4480

_exptl_crystal_description       cubic
_exptl_crystal_colour            dark
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.399
_exptl_crystal_F_000             2006
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_exptl_absorpt_coefficient_mu    0.930
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.13675
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
;
 ?
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.012 -0.009 0.358 12892 529 ' '
_platon_squeeze_details          
;
;

_diffrn_ambient_temperature      293.00(10)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.5594
_diffrn_reflns_number            23307
_diffrn_reflns_av_unetI/netI     0.0204
_diffrn_reflns_av_R_equivalents  ?
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_theta_min         3.886
_diffrn_reflns_theta_max         73.506
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3233
_reflns_number_gt                2798
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Data were apparently pre-merged, so _diffrn_reflns_number
 etc. will have to be added later.
 
 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.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_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)+(0.1315P)²] 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         3233
_refine_ls_number_parameters     83
_refine_ls_number_restraints     66
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0563
_refine_ls_wR_factor_ref         0.1637
_refine_ls_wR_factor_gt          0.1595
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_restrained_S_all      1.312
_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 0.09742(2) 1.0000 1.0000 0.01840(18) Uani 1 8 d S T P . .
O1 O 0.14053(7) 1.0000 0.92379(7) 0.0410(4) Uani 1 2 d S T P . .
O2 O 0.04799(13) 1.04799(13) 1.04799(13) 0.0717(17) Uani 1 6 d S T P . .
N1 N 0.5000 1.0000 0.5799(3) 0.127(3) Uani 1 4 d S TU P . .
C1 C 0.12409(10) 1.0000 0.87591(10) 0.0417(8) Uani 1 4 d S T P . .
C2 C 0.16578(11) 1.0000 0.83422(11) 0.0630(13) Uani 1 4 d S T P . .
C3 C 0.2163(2) 1.0000 0.8465(2) 0.121(2) Uani 1 2 d S TU P . .
H3 H 0.2260 1.0000 0.8826 0.145 Uiso 1 2 calc R U P . .
C4 C 0.2566(3) 1.0000 0.8083(3) 0.148(3) Uani 1 2 d S TU P . .
H4 H 0.2925 1.0000 0.8188 0.178 Uiso 1 2 calc R U P . .
C5 C 0.24359(18) 1.0000 0.75641(18) 0.099(2) Uani 1 4 d S TU P . .
C6 C 0.2843(2) 1.0000 0.7157(2) 0.112(3) Uani 1 4 d S TU P . .
C7 C 0.3232(4) 0.9616(4) 0.7151(4) 0.156(4) Uani 0.5 1 d . U P . .
H7 H 0.3250 0.9380 0.7441 0.187 Uiso 0.5 1 calc R U P . .
C8 C 0.3624(4) 0.9551(5) 0.6717(4) 0.177(5) Uani 0.5 1 d . U P . .
H8 H 0.3846 0.9254 0.6671 0.213 Uiso 0.5 1 calc R U P . .
C9 C 0.3614(2) 1.0000 0.6386(2) 0.112(3) Uani 1 4 d S TU P . .
C10 C 0.4040(2) 1.0000 0.5960(2) 0.117(3) Uani 1 4 d S TU P . .
C11 C 0.4567(2) 1.0000 0.6125(2) 0.145(3) Uani 1 2 d S TU P . .
C12 C 0.4738(2) 1.0000 0.6650(2) 0.156(3) Uani 1 2 d S TU P . .
H12 H 0.4518 1.0000 0.6952 0.187 Uiso 1 2 calc R U 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 O2 2.1358(19) 26_467 ?
Zr1 O2 2.1358(19) 4_465 ?
Zr1 O2 2.1358(18) 27_557 ?
Zr1 O2 2.1358(18) . ?
Zr1 O1 2.2271(17) . ?
Zr1 O1 2.2272(18) 5_575 ?
Zr1 O1 2.2272(17) 27_557 ?
Zr1 O1 2.2272(17) 7_557 ?
Zr1 Zr1 3.5048(4) 26_467 ?
Zr1 Zr1 3.5048(4) 8_456 ?
Zr1 Zr1 3.5048(4) 32_676 ?
Zr1 Zr1 3.5048(4) 2_665 ?
O1 C1 1.288(3) . ?
O2 Zr1 2.1358(18) 32_676 ?
O2 Zr1 2.1358(18) 2_665 ?
N1 C11 1.377(6) 3_675 ?
N1 C11 1.378(6) . ?
C1 O1 1.288(3) 47_656 ?
C1 C2 1.500(5) . ?
C2 C3 1.324(5) 47_656 ?
C2 C3 1.324(5) . ?
C3 C4 1.411(7) . ?
C4 C5 1.362(7) . ?
C5 C4 1.362(7) 47_656 ?
C5 C6 1.465(10) . ?
C6 C7 1.392(10) 47_656 ?
C6 C7 1.392(10) 33_575 ?
C6 C7 1.392(10) . ?
C6 C7 1.392(10) 24_676 ?
C7 C8 1.496(13) . ?
C8 C9 1.420(11) . ?
C8 C7 1.983(13) 47_656 ?
C9 C8 1.420(11) 47_656 ?
C9 C8 1.420(11) 33_575 ?
C9 C8 1.420(11) 24_676 ?
C9 C10 1.533(10) . ?
C10 C11 1.405(7) . ?
C10 C11 1.405(7) 47_656 ?
C11 C12 1.406(7) . ?
C12 C12 1.334(12) 3_675 ?

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 Zr1 O2 69.71(15) 26_467 4_465 ?
O2 Zr1 O2 69.71(15) 26_467 27_557 ?
O2 Zr1 O2 107.9(3) 4_465 27_557 ?
O2 Zr1 O2 107.9(3) 26_467 . ?
O2 Zr1 O2 69.71(15) 4_465 . ?
O2 Zr1 O2 69.71(15) 27_557 . ?
O2 Zr1 O1 78.02(12) 26_467 . ?
O2 Zr1 O1 141.94(9) 4_465 . ?
O2 Zr1 O1 78.02(12) 27_557 . ?
O2 Zr1 O1 141.94(9) . . ?
O2 Zr1 O1 141.94(9) 26_467 5_575 ?
O2 Zr1 O1 141.94(9) 4_465 5_575 ?
O2 Zr1 O1 78.02(12) 27_557 5_575 ?
O2 Zr1 O1 78.02(12) . 5_575 ?
O1 Zr1 O1 75.97(5) . 5_575 ?
O2 Zr1 O1 141.94(9) 26_467 27_557 ?
O2 Zr1 O1 78.02(12) 4_465 27_557 ?
O2 Zr1 O1 141.94(9) 27_557 27_557 ?
O2 Zr1 O1 78.02(12) . 27_557 ?
O1 Zr1 O1 121.02(10) . 27_557 ?
O1 Zr1 O1 75.98(5) 5_575 27_557 ?
O2 Zr1 O1 78.02(12) 26_467 7_557 ?
O2 Zr1 O1 78.02(12) 4_465 7_557 ?
O2 Zr1 O1 141.94(9) 27_557 7_557 ?
O2 Zr1 O1 141.94(9) . 7_557 ?
O1 Zr1 O1 75.97(5) . 7_557 ?
O1 Zr1 O1 121.02(10) 5_575 7_557 ?
O1 Zr1 O1 75.98(5) 27_557 7_557 ?
O2 Zr1 Zr1 34.87(7) 26_467 26_467 ?
O2 Zr1 Zr1 34.87(7) 4_465 26_467 ?
O2 Zr1 Zr1 89.30(13) 27_557 26_467 ?
O2 Zr1 Zr1 89.30(13) . 26_467 ?
O1 Zr1 Zr1 110.37(3) . 26_467 ?
O1 Zr1 Zr1 164.49(5) 5_575 26_467 ?
O1 Zr1 Zr1 110.37(3) 27_557 26_467 ?
O1 Zr1 Zr1 74.49(5) 7_557 26_467 ?
O2 Zr1 Zr1 34.87(7) 26_467 8_456 ?
O2 Zr1 Zr1 89.30(13) 4_465 8_456 ?
O2 Zr1 Zr1 34.87(7) 27_557 8_456 ?
O2 Zr1 Zr1 89.30(13) . 8_456 ?
O1 Zr1 Zr1 74.49(5) . 8_456 ?
O1 Zr1 Zr1 110.37(3) 5_575 8_456 ?
O1 Zr1 Zr1 164.49(5) 27_557 8_456 ?
O1 Zr1 Zr1 110.37(3) 7_557 8_456 ?
Zr1 Zr1 Zr1 60.0 26_467 8_456 ?
O2 Zr1 Zr1 89.30(13) 26_467 32_676 ?
O2 Zr1 Zr1 34.87(7) 4_465 32_676 ?
O2 Zr1 Zr1 89.30(13) 27_557 32_676 ?
O2 Zr1 Zr1 34.87(7) . 32_676 ?
O1 Zr1 Zr1 164.49(5) . 32_676 ?
O1 Zr1 Zr1 110.37(3) 5_575 32_676 ?
O1 Zr1 Zr1 74.49(5) 27_557 32_676 ?
O1 Zr1 Zr1 110.37(3) 7_557 32_676 ?
Zr1 Zr1 Zr1 60.0 26_467 32_676 ?
Zr1 Zr1 Zr1 90.0 8_456 32_676 ?
O2 Zr1 Zr1 89.30(13) 26_467 2_665 ?
O2 Zr1 Zr1 89.30(13) 4_465 2_665 ?
O2 Zr1 Zr1 34.87(7) 27_557 2_665 ?
O2 Zr1 Zr1 34.87(7) . 2_665 ?
O1 Zr1 Zr1 110.37(3) . 2_665 ?
O1 Zr1 Zr1 74.49(5) 5_575 2_665 ?
O1 Zr1 Zr1 110.37(3) 27_557 2_665 ?
O1 Zr1 Zr1 164.49(5) 7_557 2_665 ?
Zr1 Zr1 Zr1 90.0 26_467 2_665 ?
Zr1 Zr1 Zr1 60.0 8_456 2_665 ?
Zr1 Zr1 Zr1 60.0 32_676 2_665 ?
C1 O1 Zr1 131.57(18) . . ?
Zr1 O2 Zr1 110.27(14) 32_676 2_665 ?
Zr1 O2 Zr1 110.27(14) 32_676 . ?
Zr1 O2 Zr1 110.27(14) 2_665 . ?
C11 N1 C11 106.1(7) 3_675 . ?
O1 C1 O1 127.9(3) 47_656 . ?
O1 C1 C2 116.06(16) 47_656 . ?
O1 C1 C2 116.06(16) . . ?
C3 C2 C3 117.3(6) 47_656 . ?
C3 C2 C1 121.4(3) 47_656 . ?
C3 C2 C1 121.4(3) . . ?
C2 C3 C4 122.9(5) . . ?
C5 C4 C3 119.4(6) . . ?
C4 C5 C4 118.2(7) . 47_656 ?
C4 C5 C6 120.9(4) . . ?
C4 C5 C6 120.9(4) 47_656 . ?
C7 C6 C7 118.6(11) 47_656 33_575 ?
C7 C6 C7 59.4(9) 47_656 . ?
C7 C6 C7 89.3(10) 33_575 . ?
C7 C6 C7 89.3(10) 47_656 24_676 ?
C7 C6 C7 59.4(9) 33_575 24_676 ?
C7 C6 C7 118.6(11) . 24_676 ?
C7 C6 C5 120.7(6) 47_656 . ?
C7 C6 C5 120.7(6) 33_575 . ?
C7 C6 C5 120.7(6) . . ?
C7 C6 C5 120.7(6) 24_676 . ?
C6 C7 C8 124.0(10) . . ?
C9 C8 C7 109.7(10) . . ?
C9 C8 C7 87.3(7) . 47_656 ?
C7 C8 C7 44.0(7) . 47_656 ?
C8 C9 C8 51.2(10) 47_656 . ?
C8 C9 C8 132.0(12) 47_656 33_575 ?
C8 C9 C8 107.2(11) . 33_575 ?
C8 C9 C8 107.2(11) 47_656 24_676 ?
C8 C9 C8 132.0(12) . 24_676 ?
C8 C9 C8 51.2(10) 33_575 24_676 ?
C8 C9 C10 114.0(6) 47_656 . ?
C8 C9 C10 114.0(6) . . ?
C8 C9 C10 114.0(6) 33_575 . ?
C8 C9 C10 114.0(6) 24_676 . ?
C11 C10 C11 124.7(7) . 47_656 ?
C11 C10 C9 117.7(4) . . ?
C11 C10 C9 117.7(4) 47_656 . ?
N1 C11 C12 108.9(6) . . ?
N1 C11 C10 125.7(5) . . ?
C12 C11 C10 125.3(6) . . ?
C12 C12 C11 108.0(4) 3_675 . ?

_refine_diff_density_max         0.923
_refine_diff_density_min         -0.858
_refine_diff_density_rms         0.074

_shelxl_version_number           2013-4

# start Validation Reply Form
_vrf_PLAT430_1                   
;
PROBLEM: Short Inter D...A Contact  N1     ..  N1      ..       2.87 Ang.  
RESPONSE: In the porphyrin ring, two nitrogen atoms should have hydrogen 
atoms and there are strong hydrogen bonding interactions between the four 
nitrogen atoms. However, according to the high symmetry the hydrogen atoms 
can not located.
;

# end Validation Reply Form

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1043281'
_audit_update_record             
;
2015-01-13 deposited with the CCDC.
2015-03-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C216 H124 Cu3 N12 O32 Zr6'
_chemical_formula_weight         4137.20

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'
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'
Zr Zr -0.1862 2.2449 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu -1.9646 0.5888 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_H-M_alt        'P m -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'
'-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, -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'

_cell_length_a                   25.4213(2)
_cell_length_b                   25.4213(2)
_cell_length_c                   25.4213(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     16428.3(4)
_cell_formula_units_Z            1
_cell_measurement_temperature    293.00(10)
_cell_measurement_reflns_used    2990
_cell_measurement_theta_min      3.8700
_cell_measurement_theta_max      72.9050

_exptl_crystal_description       cubic
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.418
_exptl_crystal_F_000             2087
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.09
_exptl_absorpt_coefficient_mu    1.032
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.94100
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293.00(10)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.5594
_diffrn_reflns_number            16152
_diffrn_reflns_av_unetI/netI     0.0436
_diffrn_reflns_av_R_equivalents  0.0683
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_theta_min         3.888
_diffrn_reflns_theta_max         73.150
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3192
_reflns_number_gt                2496
_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.
 
 _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.
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.005 -0.003 -0.003 13161 1119 ' '
_platon_squeeze_void_probe_radius 1.20
_platon_squeeze_details          ?

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_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)+(0.1103P)²+9.8505P] 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         3192
_refine_ls_number_parameters     85
_refine_ls_number_restraints     54
_refine_ls_R_factor_all          0.0776
_refine_ls_R_factor_gt           0.0633
_refine_ls_wR_factor_ref         0.1913
_refine_ls_wR_factor_gt          0.1814
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_restrained_S_all      1.435
_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 0.5000 0.40255(2) 0.5000 0.0165(2) Uani 1 8 d S T P . .
Cu1 Cu 1.0000 0.0000 0.5000 0.154(2) Uani 1 16 d S TU P . .
O1 O 0.45064(16) 0.45064(16) 0.45064(16) 0.0504(17) Uani 1 6 d S T P . .
O2 O 0.57680(12) 0.35949(11) 0.5000 0.0355(7) Uani 1 2 d S T P . .
N1 N 0.9218(3) 0.0000 0.5000 0.131(5) Uani 1 4 d S TU P . .
C1 C 0.62437(16) 0.37563(16) 0.5000 0.0363(13) Uani 1 4 d S T P . .
C2 C 0.66609(19) 0.33391(19) 0.5000 0.056(2) Uani 1 4 d S T P . .
C3 C 0.6537(3) 0.2833(3) 0.5000 0.152(6) Uani 1 2 d S T P . .
H3 H 0.6177 0.2733 0.5000 0.182 Uiso 1 2 calc R U P . .
C4 C 0.6918(3) 0.2448(3) 0.5000 0.148(5) Uani 1 2 d S TU P . .
H4 H 0.6815 0.2089 0.5000 0.177 Uiso 1 2 calc R U P . .
C5 C 0.7433(2) 0.2567(2) 0.5000 0.095(4) Uani 1 4 d S TU P . .
C6 C 0.7855(2) 0.2145(2) 0.5000 0.149(8) Uani 1 4 d S T P . .
C7 C 0.7864(4) 0.1776(4) 0.5377(7) 0.175(10) Uani 0.5 1 d . . P . .
H7 H 0.7714 0.1471 0.5533 0.210 Uiso 0.5 1 calc R U P . .
C9 C 0.8628(3) 0.1372(3) 0.5000 0.114(5) Uani 1 4 d S TU P . .
C10 C 0.9048(3) 0.0952(3) 0.5000 0.124(5) Uani 1 4 d S TU P . .
C11 C 0.8902(3) 0.0427(3) 0.5000 0.138(4) Uani 1 2 d S TU P . .
C12 C 0.8357(3) 0.0263(3) 0.5000 0.151(4) Uani 1 2 d S TU P . .
H12 H 0.8057 0.0486 0.5000 0.181 Uiso 1 2 calc R U P . .
C8 C 0.8260(5) 0.1399(4) 0.5444(7) 0.151(6) Uani 0.5 1 d . U P . .
H8 H 0.8263 0.1027 0.5477 0.182 Uiso 0.5 1 calc R U 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 O1 2.155(3) 28_656 ?
Zr1 O1 2.155(2) . ?
Zr1 O1 2.155(2) 27_556 ?
Zr1 O1 2.155(3) 2_655 ?
Zr1 O2 2.238(3) 8_556 ?
Zr1 O2 2.238(3) 30_655 ?
Zr1 O2 2.238(3) 10_655 ?
Zr1 O2 2.238(3) . ?
Zr1 Zr1 3.5033(8) 29_656 ?
Zr1 Zr1 3.5033(8) 2_655 ?
Zr1 Zr1 3.5033(8) 26_566 ?
Zr1 Zr1 3.5033(8) 5_565 ?
Cu1 N1 1.989(7) 26_666 ?
Cu1 N1 1.989(7) 2_645 ?
Cu1 N1 1.989(7) 25_756 ?
Cu1 N1 1.989(7) . ?
O1 Zr1 2.155(3) 5_565 ?
O1 Zr1 2.155(2) 26_566 ?
O2 C1 1.277(4) . ?
N1 C11 1.350(8) . ?
N1 C11 1.350(8) 6_556 ?
C1 O2 1.277(4) 43_665 ?
C1 C2 1.500(9) . ?
C2 C3 1.325(8) . ?
C2 C3 1.325(8) 43_665 ?
C3 C4 1.379(9) . ?
C4 C5 1.343(9) . ?
C5 C4 1.343(9) 43_665 ?
C5 C6 1.519(11) . ?
C6 C7 1.342(14) . ?
C6 C7 1.342(14) 43_665 ?
C6 C7 1.342(14) 27_556 ?
C6 C7 1.342(14) 20_666 ?
C7 C7 1.30(2) 43_665 ?
C7 C8 1.400(14) . ?
C7 C8 1.883(15) 43_665 ?
C7 C7 1.92(4) 27_556 ?
C9 C8 1.468(15) 43_665 ?
C9 C8 1.468(15) 20_666 ?
C9 C8 1.468(15) 27_556 ?
C9 C8 1.468(15) . ?
C9 C10 1.510(13) . ?
C10 C11 1.385(8) . ?
C10 C11 1.385(8) 43_665 ?
C11 C12 1.446(9) . ?
C12 C12 1.340(15) 6_556 ?
C8 C8 1.22(2) 43_665 ?
C8 C7 1.883(15) 43_665 ?

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
O1 Zr1 O1 110.9(4) 28_656 . ?
O1 Zr1 O1 71.22(18) 28_656 27_556 ?
O1 Zr1 O1 71.22(18) . 27_556 ?
O1 Zr1 O1 71.22(18) 28_656 2_655 ?
O1 Zr1 O1 71.22(18) . 2_655 ?
O1 Zr1 O1 110.9(4) 27_556 2_655 ?
O1 Zr1 O2 141.75(3) 28_656 8_556 ?
O1 Zr1 O2 76.68(15) . 8_556 ?
O1 Zr1 O2 141.75(3) 27_556 8_556 ?
O1 Zr1 O2 76.68(15) 2_655 8_556 ?
O1 Zr1 O2 141.75(3) 28_656 30_655 ?
O1 Zr1 O2 76.68(15) . 30_655 ?
O1 Zr1 O2 76.68(15) 27_556 30_655 ?
O1 Zr1 O2 141.75(3) 2_655 30_655 ?
O2 Zr1 O2 76.16(7) 8_556 30_655 ?
O1 Zr1 O2 76.68(15) 28_656 10_655 ?
O1 Zr1 O2 141.75(3) . 10_655 ?
O1 Zr1 O2 76.68(15) 27_556 10_655 ?
O1 Zr1 O2 141.75(3) 2_655 10_655 ?
O2 Zr1 O2 121.44(16) 8_556 10_655 ?
O2 Zr1 O2 76.16(7) 30_655 10_655 ?
O1 Zr1 O2 76.68(15) 28_656 . ?
O1 Zr1 O2 141.75(3) . . ?
O1 Zr1 O2 141.75(3) 27_556 . ?
O1 Zr1 O2 76.68(15) 2_655 . ?
O2 Zr1 O2 76.16(7) 8_556 . ?
O2 Zr1 O2 121.44(16) 30_655 . ?
O2 Zr1 O2 76.16(7) 10_655 . ?
O1 Zr1 Zr1 35.62(9) 28_656 29_656 ?
O1 Zr1 Zr1 90.61(16) . 29_656 ?
O1 Zr1 Zr1 35.62(9) 27_556 29_656 ?
O1 Zr1 Zr1 90.61(16) 2_655 29_656 ?
O2 Zr1 Zr1 164.28(8) 8_556 29_656 ?
O2 Zr1 Zr1 110.23(5) 30_655 29_656 ?
O2 Zr1 Zr1 74.28(8) 10_655 29_656 ?
O2 Zr1 Zr1 110.23(5) . 29_656 ?
O1 Zr1 Zr1 35.62(9) 28_656 2_655 ?
O1 Zr1 Zr1 90.61(16) . 2_655 ?
O1 Zr1 Zr1 90.61(16) 27_556 2_655 ?
O1 Zr1 Zr1 35.62(9) 2_655 2_655 ?
O2 Zr1 Zr1 110.23(5) 8_556 2_655 ?
O2 Zr1 Zr1 164.28(8) 30_655 2_655 ?
O2 Zr1 Zr1 110.23(5) 10_655 2_655 ?
O2 Zr1 Zr1 74.28(8) . 2_655 ?
Zr1 Zr1 Zr1 60.0 29_656 2_655 ?
O1 Zr1 Zr1 90.61(16) 28_656 26_566 ?
O1 Zr1 Zr1 35.62(9) . 26_566 ?
O1 Zr1 Zr1 35.62(9) 27_556 26_566 ?
O1 Zr1 Zr1 90.61(16) 2_655 26_566 ?
O2 Zr1 Zr1 110.23(5) 8_556 26_566 ?
O2 Zr1 Zr1 74.28(8) 30_655 26_566 ?
O2 Zr1 Zr1 110.23(5) 10_655 26_566 ?
O2 Zr1 Zr1 164.28(8) . 26_566 ?
Zr1 Zr1 Zr1 60.0 29_656 26_566 ?
Zr1 Zr1 Zr1 90.000(1) 2_655 26_566 ?
O1 Zr1 Zr1 90.61(16) 28_656 5_565 ?
O1 Zr1 Zr1 35.62(9) . 5_565 ?
O1 Zr1 Zr1 90.61(16) 27_556 5_565 ?
O1 Zr1 Zr1 35.62(9) 2_655 5_565 ?
O2 Zr1 Zr1 74.28(8) 8_556 5_565 ?
O2 Zr1 Zr1 110.23(5) 30_655 5_565 ?
O2 Zr1 Zr1 164.28(8) 10_655 5_565 ?
O2 Zr1 Zr1 110.23(5) . 5_565 ?
Zr1 Zr1 Zr1 90.000(1) 29_656 5_565 ?
Zr1 Zr1 Zr1 60.0 2_655 5_565 ?
Zr1 Zr1 Zr1 60.0 26_566 5_565 ?
N1 Cu1 N1 180.0 26_666 2_645 ?
N1 Cu1 N1 90.000(1) 26_666 25_756 ?
N1 Cu1 N1 90.0 2_645 25_756 ?
N1 Cu1 N1 90.0 26_666 . ?
N1 Cu1 N1 90.000(1) 2_645 . ?
N1 Cu1 N1 180.0 25_756 . ?
Zr1 O1 Zr1 108.76(18) . 5_565 ?
Zr1 O1 Zr1 108.76(18) . 26_566 ?
Zr1 O1 Zr1 108.76(18) 5_565 26_566 ?
C1 O2 Zr1 132.0(3) . . ?
C11 N1 C11 107.0(8) . 6_556 ?
C11 N1 Cu1 126.5(4) . . ?
C11 N1 Cu1 126.5(4) 6_556 . ?
O2 C1 O2 127.5(5) . 43_665 ?
O2 C1 C2 116.3(3) . . ?
O2 C1 C2 116.3(3) 43_665 . ?
C3 C2 C3 117.6(8) . 43_665 ?
C3 C2 C1 121.2(4) . . ?
C3 C2 C1 121.2(4) 43_665 . ?
C2 C3 C4 121.5(7) . . ?
C5 C4 C3 121.7(8) . . ?
C4 C5 C4 116.1(9) . 43_665 ?
C4 C5 C6 121.9(4) . . ?
C4 C5 C6 121.9(4) 43_665 . ?
C7 C6 C7 57.7(12) . 43_665 ?
C7 C6 C7 91.3(14) . 27_556 ?
C7 C6 C7 119.3(13) 43_665 27_556 ?
C7 C6 C7 119.3(13) . 20_666 ?
C7 C6 C7 91.3(15) 43_665 20_666 ?
C7 C6 C7 57.7(12) 27_556 20_666 ?
C7 C6 C5 120.4(7) . . ?
C7 C6 C5 120.4(7) 43_665 . ?
C7 C6 C5 120.4(7) 27_556 . ?
C7 C6 C5 120.4(7) 20_666 . ?
C7 C7 C6 61.1(6) 43_665 . ?
C7 C7 C8 88.6(7) 43_665 . ?
C6 C7 C8 125.2(14) . . ?
C7 C7 C8 48.0(5) 43_665 43_665 ?
C6 C7 C8 96.6(9) . 43_665 ?
C8 C7 C8 40.6(9) . 43_665 ?
C7 C7 C7 90.005(2) 43_665 27_556 ?
C6 C7 C7 44.4(7) . 27_556 ?
C8 C7 C7 97.0(11) . 27_556 ?
C8 C7 C7 95.2(8) 43_665 27_556 ?
C8 C9 C8 100.6(13) 43_665 20_666 ?
C8 C9 C8 122.1(12) 43_665 27_556 ?
C8 C9 C8 49.3(11) 20_666 27_556 ?
C8 C9 C8 49.3(11) 43_665 . ?
C8 C9 C8 122.1(12) 20_666 . ?
C8 C9 C8 100.6(13) 27_556 . ?
C8 C9 C10 118.9(6) 43_665 . ?
C8 C9 C10 118.9(6) 20_666 . ?
C8 C9 C10 118.9(6) 27_556 . ?
C8 C9 C10 118.9(6) . . ?
C11 C10 C11 121.2(9) . 43_665 ?
C11 C10 C9 119.4(4) . . ?
C11 C10 C9 119.4(4) 43_665 . ?
N1 C11 C10 127.9(7) . . ?
N1 C11 C12 109.8(6) . . ?
C10 C11 C12 122.3(7) . . ?
C12 C12 C11 106.7(4) 6_556 . ?
C8 C8 C7 91.4(7) 43_665 . ?
C8 C8 C9 65.3(5) 43_665 . ?
C7 C8 C9 113.4(14) . . ?
C8 C8 C7 48.0(5) 43_665 43_665 ?
C7 C8 C7 43.4(8) . 43_665 ?
C9 C8 C7 90.5(9) . 43_665 ?

_refine_diff_density_max         1.514
_refine_diff_density_min         -1.605
_refine_diff_density_rms         0.086

_shelxl_version_number           2013-4


# start Validation Reply Form
_vrf_PLAT213_1                   
;                                                                         
PROBLEM:  Atom Cu1             has ADP max/min Ratio .....        4.8 prolat  
          Atom C6              has ADP max/min Ratio .....        4.4 prolat  
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, the diffraction of the crystal is still weak.
;
_vrf_PLAT242_1                   
;
PROBLEM: Low       Ueq as Compared to Neighbors for .....         C5 Check 
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, the diffraction of the crystal is still weak.
;
_vrf_PLAT250_1                   
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        9.0 Note
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, the diffraction of the crystal is still weak.
;
_vrf_PLAT326_1                   
;
PROBLEM: Possible Missing H on sp3? Carbon ..............         C9 Check  
RESPONSE: The C9 atom is an sp2 acrbon rather than sp3 carbon. Due to the 
disorder of the adjacent C8 atom, C9 seems to be an sp3 carbon.
;

# end Validation Reply Form
####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1043914'
_audit_update_record             
;
2015-01-16 deposited with the CCDC.
2015-03-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C216 H130 Hf6 N12 O32'
_chemical_formula_weight         4476.25

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'
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'
Hf Hf -6.1794 4.9776 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_H-M_alt        'P m -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'
'-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, -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'

_cell_length_a                   25.39760(10)
_cell_length_b                   25.39760(10)
_cell_length_c                   25.39760(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     16382.42(19)
_cell_formula_units_Z            1
_cell_measurement_temperature    293.00(10)
_cell_measurement_reflns_used    17090
_cell_measurement_theta_min      3.8770
_cell_measurement_theta_max      73.2370

_exptl_crystal_description       cubic
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.454
_exptl_crystal_F_000             2198
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.13
_exptl_absorpt_coefficient_mu    1.876
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.34212
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
 ?
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.005 -0.003 -0.003 13079 3615 ' '
_platon_squeeze_details          
;
;
_diffrn_ambient_temperature      293.00(10)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.5594
_diffrn_reflns_number            29548
_diffrn_reflns_av_unetI/netI     0.0165
_diffrn_reflns_av_R_equivalents  ?
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_theta_min         3.014
_diffrn_reflns_theta_max         73.231
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3164
_reflns_number_gt                2744
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Data were apparently pre-merged, so _diffrn_reflns_number
 etc. will have to be added later.
 
 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.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_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)+(0.0740P)²+0.9793P] 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         3164
_refine_ls_number_parameters     83
_refine_ls_number_restraints     24
_refine_ls_R_factor_all          0.0330
_refine_ls_R_factor_gt           0.0306
_refine_ls_wR_factor_ref         0.1032
_refine_ls_wR_factor_gt          0.1019
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_restrained_S_all      1.157
_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 0.5000 0.5000 0.40309(2) 0.01883(11) Uani 1 8 d S T P . .
O2 O 0.42384(8) 0.5000 0.36013(8) 0.0383(5) Uani 1 2 d S T P . .
O1 O 0.45239(13) 0.54761(13) 0.45239(13) 0.0658(17) Uani 1 6 d S T P . .
C1 C 0.37645(11) 0.5000 0.37645(11) 0.0427(11) Uani 1 4 d S T P . .
C5 C 0.25653(18) 0.5000 0.25653(18) 0.127(4) Uani 1 4 d S T P . .
C6 C 0.2149(2) 0.5000 0.2149(2) 0.141(5) Uani 1 4 d S T P . .
C2 C 0.33436(13) 0.5000 0.33436(13) 0.0640(16) Uani 1 4 d S T P . .
C3 C 0.28395(19) 0.5000 0.34741(18) 0.150(3) Uani 1 2 d S T P . .
H3 H 0.2743 0.5000 0.3835 0.180 Uiso 1 2 calc R U P . .
C10 C 0.09569(19) 0.5000 0.09569(19) 0.214(8) Uani 1 4 d S TU P . .
C9 C 0.1384(2) 0.5000 0.1384(2) 0.122(3) Uani 1 4 d S TU P . .
C11 C 0.0429(2) 0.5000 0.11111(19) 0.219(6) Uani 1 2 d S TU P . .
C12 C 0.0268(2) 0.5000 0.1648(2) 0.277(7) Uani 1 2 d S TU P . .
H12 H 0.0491 0.5000 0.1948 0.333 Uiso 1 2 calc R U P . .
C4 C 0.2446(2) 0.5000 0.3088(2) 0.200(5) Uani 1 2 d S T P . .
H4 H 0.2087 0.5000 0.3193 0.240 Uiso 1 2 calc R U P . .
C7 C 0.1788(3) 0.4591(6) 0.2131(3) 0.223(9) Uani 0.5 1 d . . P . .
H7 H 0.1799 0.4318 0.2386 0.268 Uiso 0.5 1 calc R U P . .
C8 C 0.1404(3) 0.4585(5) 0.1731(3) 0.172(5) Uani 0.5 1 d . . P . .
H8 H 0.1164 0.4300 0.1701 0.207 Uiso 0.5 1 calc R U P . .
N1 N 0.0000 0.5000 0.0804(2) 0.211(7) Uani 1 4 d S T 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 O1 2.1195(18) . ?
Hf1 O1 2.1195(18) 4_565 ?
Hf1 O1 2.1195(18) 3_665 ?
Hf1 O1 2.1195(18) 2_655 ?
Hf1 O2 2.221(2) 2_655 ?
Hf1 O2 2.221(2) 4_565 ?
Hf1 O2 2.221(2) 3_665 ?
Hf1 O2 2.221(2) . ?
Hf1 Hf1 3.4807(3) 5_565 ?
Hf1 Hf1 3.4807(3) 32_665 ?
Hf1 Hf1 3.4807(3) 8_556 ?
Hf1 Hf1 3.4807(3) 29_656 ?
O2 C1 1.273(3) . ?
O1 Hf1 2.1195(18) 5_565 ?
O1 Hf1 2.1195(18) 8_556 ?
C1 O2 1.273(3) 23_565 ?
C1 C2 1.512(6) . ?
C5 C4 1.361(6) . ?
C5 C4 1.361(6) 23_565 ?
C5 C6 1.496(9) . ?
C6 C7 1.386(11) 48 ?
C6 C7 1.386(11) . ?
C6 C7 1.386(11) 33_565 ?
C6 C7 1.386(11) 23_565 ?
C2 C3 1.323(5) 23_565 ?
C2 C3 1.323(5) . ?
C3 C4 1.400(7) . ?
C3 H3 0.9500 . ?
C10 C11 1.396(6) 23_565 ?
C10 C11 1.396(6) . ?
C10 C9 1.534(10) . ?
C9 C8 1.373(10) 23_565 ?
C9 C8 1.373(10) 33_565 ?
C9 C8 1.373(10) 48 ?
C9 C8 1.373(10) . ?
C11 N1 1.341(6) . ?
C11 C12 1.423(7) . ?
C12 C12 1.361(11) 3_565 ?
C12 H12 0.9500 . ?
C4 H4 0.9500 . ?
C7 C8 1.408(9) . ?
C7 H7 0.9500 . ?
C8 C7 1.852(11) 48 ?
C8 H8 0.9500 . ?
N1 C11 1.341(6) 3_565 ?

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
O1 Hf1 O1 69.58(15) . 4_565 ?
O1 Hf1 O1 107.6(3) . 3_665 ?
O1 Hf1 O1 69.58(15) 4_565 3_665 ?
O1 Hf1 O1 69.58(15) . 2_655 ?
O1 Hf1 O1 107.6(3) 4_565 2_655 ?
O1 Hf1 O1 69.58(15) 3_665 2_655 ?
O1 Hf1 O2 141.92(2) . 2_655 ?
O1 Hf1 O2 141.92(2) 4_565 2_655 ?
O1 Hf1 O2 78.07(12) 3_665 2_655 ?
O1 Hf1 O2 78.07(12) 2_655 2_655 ?
O1 Hf1 O2 78.07(12) . 4_565 ?
O1 Hf1 O2 78.07(12) 4_565 4_565 ?
O1 Hf1 O2 141.92(2) 3_665 4_565 ?
O1 Hf1 O2 141.92(2) 2_655 4_565 ?
O2 Hf1 O2 121.14(11) 2_655 4_565 ?
O1 Hf1 O2 141.92(2) . 3_665 ?
O1 Hf1 O2 78.07(12) 4_565 3_665 ?
O1 Hf1 O2 78.07(12) 3_665 3_665 ?
O1 Hf1 O2 141.92(2) 2_655 3_665 ?
O2 Hf1 O2 76.03(5) 2_655 3_665 ?
O2 Hf1 O2 76.03(5) 4_565 3_665 ?
O1 Hf1 O2 78.07(12) . . ?
O1 Hf1 O2 141.92(2) 4_565 . ?
O1 Hf1 O2 141.92(2) 3_665 . ?
O1 Hf1 O2 78.07(12) 2_655 . ?
O2 Hf1 O2 76.03(5) 2_655 . ?
O2 Hf1 O2 76.03(5) 4_565 . ?
O2 Hf1 O2 121.14(11) 3_665 . ?
O1 Hf1 Hf1 34.80(7) . 5_565 ?
O1 Hf1 Hf1 34.80(7) 4_565 5_565 ?
O1 Hf1 Hf1 89.19(12) 3_665 5_565 ?
O1 Hf1 Hf1 89.19(12) 2_655 5_565 ?
O2 Hf1 Hf1 164.43(6) 2_655 5_565 ?
O2 Hf1 Hf1 74.43(6) 4_565 5_565 ?
O2 Hf1 Hf1 110.33(4) 3_665 5_565 ?
O2 Hf1 Hf1 110.33(4) . 5_565 ?
O1 Hf1 Hf1 89.18(12) . 32_665 ?
O1 Hf1 Hf1 34.80(7) 4_565 32_665 ?
O1 Hf1 Hf1 34.80(7) 3_665 32_665 ?
O1 Hf1 Hf1 89.19(12) 2_655 32_665 ?
O2 Hf1 Hf1 110.33(4) 2_655 32_665 ?
O2 Hf1 Hf1 110.33(4) 4_565 32_665 ?
O2 Hf1 Hf1 74.43(6) 3_665 32_665 ?
O2 Hf1 Hf1 164.43(6) . 32_665 ?
Hf1 Hf1 Hf1 60.0 5_565 32_665 ?
O1 Hf1 Hf1 34.80(7) . 8_556 ?
O1 Hf1 Hf1 89.19(12) 4_565 8_556 ?
O1 Hf1 Hf1 89.19(12) 3_665 8_556 ?
O1 Hf1 Hf1 34.80(7) 2_655 8_556 ?
O2 Hf1 Hf1 110.33(4) 2_655 8_556 ?
O2 Hf1 Hf1 110.33(4) 4_565 8_556 ?
O2 Hf1 Hf1 164.43(6) 3_665 8_556 ?
O2 Hf1 Hf1 74.43(6) . 8_556 ?
Hf1 Hf1 Hf1 60.0 5_565 8_556 ?
Hf1 Hf1 Hf1 90.0 32_665 8_556 ?
O1 Hf1 Hf1 89.18(12) . 29_656 ?
O1 Hf1 Hf1 89.19(12) 4_565 29_656 ?
O1 Hf1 Hf1 34.80(7) 3_665 29_656 ?
O1 Hf1 Hf1 34.80(7) 2_655 29_656 ?
O2 Hf1 Hf1 74.43(6) 2_655 29_656 ?
O2 Hf1 Hf1 164.43(6) 4_565 29_656 ?
O2 Hf1 Hf1 110.33(4) 3_665 29_656 ?
O2 Hf1 Hf1 110.33(4) . 29_656 ?
Hf1 Hf1 Hf1 90.0 5_565 29_656 ?
Hf1 Hf1 Hf1 60.0 32_665 29_656 ?
Hf1 Hf1 Hf1 60.0 8_556 29_656 ?
C1 O2 Hf1 131.6(2) . . ?
Hf1 O1 Hf1 110.40(14) 5_565 8_556 ?
Hf1 O1 Hf1 110.40(14) 5_565 . ?
Hf1 O1 Hf1 110.40(14) 8_556 . ?
O2 C1 O2 128.0(4) . 23_565 ?
O2 C1 C2 115.99(18) . . ?
O2 C1 C2 115.99(18) 23_565 . ?
C4 C5 C4 115.7(7) . 23_565 ?
C4 C5 C6 122.2(3) . . ?
C4 C5 C6 122.2(3) 23_565 . ?
C7 C6 C7 52.8(8) 48 . ?
C7 C6 C7 121.1(10) 48 33_565 ?
C7 C6 C7 97.0(10) . 33_565 ?
C7 C6 C7 97.0(10) 48 23_565 ?
C7 C6 C7 121.1(10) . 23_565 ?
C7 C6 C7 52.8(8) 33_565 23_565 ?
C7 C6 C5 119.4(5) 48 . ?
C7 C6 C5 119.4(5) . . ?
C7 C6 C5 119.4(5) 33_565 . ?
C7 C6 C5 119.4(5) 23_565 . ?
C3 C2 C3 119.0(6) 23_565 . ?
C3 C2 C1 120.5(3) 23_565 . ?
C3 C2 C1 120.5(3) . . ?
C2 C3 C4 121.0(5) . . ?
C2 C3 H3 119.5 . . ?
C4 C3 H3 119.5 . . ?
C11 C10 C11 122.6(6) 23_565 . ?
C11 C10 C9 118.7(3) 23_565 . ?
C11 C10 C9 118.7(3) . . ?
C8 C9 C8 50.6(8) 23_565 33_565 ?
C8 C9 C8 100.1(9) 23_565 48 ?
C8 C9 C8 122.7(10) 33_565 48 ?
C8 C9 C8 122.7(10) 23_565 . ?
C8 C9 C8 100.1(9) 33_565 . ?
C8 C9 C8 50.6(8) 48 . ?
C8 C9 C10 118.6(5) 23_565 . ?
C8 C9 C10 118.6(5) 33_565 . ?
C8 C9 C10 118.6(5) 48 . ?
C8 C9 C10 118.6(5) . . ?
N1 C11 C10 128.1(5) . . ?
N1 C11 C12 108.9(5) . . ?
C10 C11 C12 123.0(5) . . ?
C12 C12 C11 106.7(3) 3_565 . ?
C12 C12 H12 126.6 3_565 . ?
C11 C12 H12 126.6 . . ?
C5 C4 C3 121.7(5) . . ?
C5 C4 H4 119.2 . . ?
C3 C4 H4 119.2 . . ?
C6 C7 C8 119.3(11) . . ?
C6 C7 H7 120.3 . . ?
C8 C7 H7 120.3 . . ?
C9 C8 C7 118.7(10) . . ?
C9 C8 C7 94.6(7) . 48 ?
C7 C8 C7 41.7(5) . 48 ?
C9 C8 H8 120.6 . . ?
C7 C8 H8 120.6 . . ?
C7 C8 H8 130.8 48 . ?
C11 N1 C11 108.8(6) . 3_565 ?

_refine_diff_density_max         0.825
_refine_diff_density_min         -0.565
_refine_diff_density_rms         0.060

_shelxl_version_number           2013-4

# start Validation Reply Form
_vrf_PLAT213_1                   
;                                                                         
PROBLEM:  Atom N1              has ADP max/min Ratio .....        4.5 prolat 
          Atom C4              has ADP max/min Ratio .....        4.8 prolat
          Atom C10             has ADP max/min Ratio .....        4.4 prolat
          Atom C11             has ADP max/min Ratio .....        4.5 prolat
          Atom C12             has ADP max/min Ratio .....        4.8 prolat

RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. 
;
_vrf_PLAT215_1                   
;
PROBLEM: Disordered C7        has ADP max/min Ratio .....        4.2    
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, C7 has large ADP max/min Ratio.
;
_vrf_PLAT220_1                   
;
PROBLEM:  Large Non-Solvent  C     Ueq(max)/Ueq(min) Range        6.5 Ratio 
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, some C atoms such as C7 have large  
Ueq(max)/Ueq(min) Range.
;
_vrf_PLAT234_1                   
;
PROBLEM: Large Hirshfeld Difference C6     --  C7      ..       0.27 Ang. 
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, C7 has large ADP max/min Ratio, whcih may lead
to the large Hirshfeld Difference.
;
_vrf_PLAT241_1                   
;
PROBLEM: High      Ueq as Compared to Neighbors for .....         C4 Check 
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, C7 has high Ueq.
;
_vrf_PLAT242_1                   
;
PROBLEM: Low Ueq as Compared to Neighbors for .....         C9 Check 
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. 
;
_vrf_PLAT250_1                   
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        9.0 Note
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, the diffraction of the crystal is still weak.
;
_vrf_PLAT430_1                   
;
PROBLEM: Short Inter D...A Contact  N1     ..  N1      ..       2.89 Ang.
RESPONSE: In the porphyrin ring, two nitrogen atoms should have hydrogen 
atoms and there are strong hydrogen bonding interactions between the four 
nitrogen atoms. However, according to the high symmetry the hydrogen atoms 
can not located.
;

# end Validation Reply Form
####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1043915'
_audit_update_record             
;
2015-01-16 deposited with the CCDC.
2015-03-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C216 H124 Cu3 Hf6 N12 O32'
_chemical_formula_weight         4660.82

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'
Cu Cu -1.9646 0.5888 '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'
Hf Hf -6.1794 4.9776 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_H-M_alt        'P m -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'
'-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, -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'

_cell_length_a                   25.35700(10)
_cell_length_b                   25.35700(10)
_cell_length_c                   25.35700(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     16303.98(19)
_cell_formula_units_Z            1
_cell_measurement_temperature    293.01(10)
_cell_measurement_reflns_used    6750
_cell_measurement_theta_min      3.8780
_cell_measurement_theta_max      73.1880

_exptl_crystal_description       cubic
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.475
_exptl_crystal_F_000             2279
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_exptl_absorpt_coefficient_mu    1.985
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.71569
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
 ?
;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.011 -0.008 0.344 13062 2065 ' '
_platon_squeeze_void_probe_radius 1.20
_platon_squeeze_details          ?

_diffrn_ambient_temperature      293.01(10)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.5594
_diffrn_reflns_number            13996
_diffrn_reflns_av_unetI/netI     0.0221
_diffrn_reflns_av_R_equivalents  0.0290
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_theta_min         3.898
_diffrn_reflns_theta_max         73.441
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             3165
_reflns_number_gt                2873
_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.
 
 _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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_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)+(0.0825P)²+7.2470P] 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         3165
_refine_ls_number_parameters     85
_refine_ls_number_restraints     30
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0397
_refine_ls_wR_factor_ref         0.1203
_refine_ls_wR_factor_gt          0.1188
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_restrained_S_all      1.545
_refine_ls_shift/su_max          0.002
_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 0.0000 0.90298(2) 1.0000 0.01509(13) Uani 1 8 d S T P . .
O2 O 0.0000 0.86033(10) 0.92368(10) 0.0341(5) Uani 1 2 d S T P . .
O1 O 0.04792(16) 0.95208(16) 0.95208(16) 0.0577(19) Uani 1 6 d S T P . .
C11 C 0.0000 0.5428(3) 0.6107(2) 0.125(3) Uani 1 2 d S TU P . .
C1 C 0.0000 0.87631(14) 0.87631(14) 0.0367(11) Uani 1 4 d S T P . .
C2 C 0.0000 0.83456(16) 0.83456(16) 0.0547(17) Uani 1 4 d S T P . .
C3 C 0.0000 0.7832(2) 0.8474(2) 0.147(5) Uani 1 2 d S T P . .
H3 H 0.0000 0.7730 0.8835 0.177 Uiso 1 2 calc R U P . .
C4 C 0.0000 0.7446(2) 0.8083(3) 0.181(7) Uani 1 2 d S T P . .
H4 H 0.0000 0.7085 0.8183 0.217 Uiso 1 2 calc R U P . .
N1 N 0.0000 0.5000 0.5779(3) 0.111(3) Uani 1 4 d S TU P . .
C5 C 0.0000 0.7571(2) 0.7571(2) 0.108(4) Uani 1 4 d S T P . .
C6 C 0.0000 0.7152(2) 0.7152(2) 0.129(6) Uani 1 4 d S T P . .
C9 C 0.0000 0.6374(3) 0.6374(3) 0.099(3) Uani 1 4 d S TU P . .
C8 C 0.0411(9) 0.6735(4) 0.6387(4) 0.238(15) Uani 0.5 1 d . . P . .
H8 H 0.0698 0.6711 0.6147 0.285 Uiso 0.5 1 calc R U P . .
Cu1 Cu 0.0000 0.5000 0.5000 0.167(2) Uani 1 16 d S TU P . .
C10 C 0.0000 0.5962(2) 0.5962(2) 0.171(9) Uani 1 4 d S T P . .
C12 C 0.0000 0.5273(3) 0.6645(3) 0.146(3) Uani 1 2 d S TU P . .
H12 H 0.0000 0.5498 0.6944 0.176 Uiso 1 2 calc R U P . .
C7 C 0.0389(7) 0.7138(4) 0.6767(4) 0.193(10) Uani 0.5 1 d . . P . .
H7 H 0.0648 0.7408 0.6760 0.231 Uiso 0.5 1 calc R U 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 O1 2.122(2) . ?
Hf1 O1 2.122(2) 27_557 ?
Hf1 O1 2.122(2) 4_465 ?
Hf1 O1 2.122(2) 26_467 ?
Hf1 O2 2.217(2) . ?
Hf1 O2 2.217(2) 8_456 ?
Hf1 O2 2.217(2) 10_656 ?
Hf1 O2 2.217(2) 27_557 ?
Hf1 Hf1 3.4789(3) 2_665 ?
Hf1 Hf1 3.4789(3) 29_557 ?
Hf1 Hf1 3.4789(3) 26_467 ?
Hf1 Hf1 3.4789(3) 5_575 ?
O2 C1 1.268(4) . ?
O1 Hf1 2.122(2) 2_665 ?
O1 Hf1 2.122(2) 5_575 ?
C11 N1 1.367(7) . ?
C11 C10 1.403(8) . ?
C11 C12 1.420(9) . ?
C1 O2 1.268(4) 21 ?
C1 C2 1.497(7) . ?
C2 C3 1.343(7) . ?
C2 C3 1.344(7) 21 ?
C3 C4 1.393(7) . ?
C3 H3 0.9500 . ?
C4 C5 1.336(8) . ?
C4 H4 0.9500 . ?
N1 C11 1.367(7) 3_565 ?
N1 Cu1 1.974(7) . ?
C5 C4 1.336(8) 21 ?
C5 C6 1.502(10) . ?
C6 C7 1.388(14) 21 ?
C6 C7 1.388(14) 30 ?
C6 C7 1.388(14) 46 ?
C6 C7 1.388(14) . ?
C9 C8 1.388(17) 30 ?
C9 C8 1.388(17) 21 ?
C9 C8 1.388(17) . ?
C9 C8 1.388(17) 46 ?
C9 C10 1.477(12) . ?
C8 C7 1.406(12) . ?
C8 H8 0.9500 . ?
Cu1 N1 1.974(7) 29_556 ?
Cu1 N1 1.974(7) 5_565 ?
Cu1 N1 1.974(7) 25_566 ?
C10 C11 1.403(8) 21 ?
C12 C12 1.384(15) 3_565 ?
C12 H12 0.9500 . ?
C7 C8 1.906(13) 46 ?
C7 C7 1.97(4) 30 ?
C7 H7 0.9500 . ?

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
O1 Hf1 O1 69.86(18) . 27_557 ?
O1 Hf1 O1 69.86(18) . 4_465 ?
O1 Hf1 O1 108.2(4) 27_557 4_465 ?
O1 Hf1 O1 108.2(4) . 26_467 ?
O1 Hf1 O1 69.87(18) 27_557 26_467 ?
O1 Hf1 O1 69.87(18) 4_465 26_467 ?
O1 Hf1 O2 77.67(15) . . ?
O1 Hf1 O2 141.82(3) 27_557 . ?
O1 Hf1 O2 77.67(15) 4_465 . ?
O1 Hf1 O2 141.82(3) 26_467 . ?
O1 Hf1 O2 141.82(3) . 8_456 ?
O1 Hf1 O2 141.82(3) 27_557 8_456 ?
O1 Hf1 O2 77.67(15) 4_465 8_456 ?
O1 Hf1 O2 77.67(15) 26_467 8_456 ?
O2 Hf1 O2 76.23(6) . 8_456 ?
O1 Hf1 O2 77.67(15) . 10_656 ?
O1 Hf1 O2 77.67(15) 27_557 10_656 ?
O1 Hf1 O2 141.82(3) 4_465 10_656 ?
O1 Hf1 O2 141.82(3) 26_467 10_656 ?
O2 Hf1 O2 76.23(6) . 10_656 ?
O2 Hf1 O2 121.60(14) 8_456 10_656 ?
O1 Hf1 O2 141.82(3) . 27_557 ?
O1 Hf1 O2 77.67(15) 27_557 27_557 ?
O1 Hf1 O2 141.82(3) 4_465 27_557 ?
O1 Hf1 O2 77.67(15) 26_467 27_557 ?
O2 Hf1 O2 121.60(14) . 27_557 ?
O2 Hf1 O2 76.23(6) 8_456 27_557 ?
O2 Hf1 O2 76.23(6) 10_656 27_557 ?
O1 Hf1 Hf1 34.94(9) . 2_665 ?
O1 Hf1 Hf1 34.94(9) 27_557 2_665 ?
O1 Hf1 Hf1 89.43(16) 4_465 2_665 ?
O1 Hf1 Hf1 89.43(16) 26_467 2_665 ?
O2 Hf1 Hf1 110.18(5) . 2_665 ?
O2 Hf1 Hf1 164.20(7) 8_456 2_665 ?
O2 Hf1 Hf1 74.20(7) 10_656 2_665 ?
O2 Hf1 Hf1 110.18(5) 27_557 2_665 ?
O1 Hf1 Hf1 89.43(15) . 29_557 ?
O1 Hf1 Hf1 34.94(9) 27_557 29_557 ?
O1 Hf1 Hf1 89.43(15) 4_465 29_557 ?
O1 Hf1 Hf1 34.94(9) 26_467 29_557 ?
O2 Hf1 Hf1 164.20(7) . 29_557 ?
O2 Hf1 Hf1 110.18(5) 8_456 29_557 ?
O2 Hf1 Hf1 110.18(5) 10_656 29_557 ?
O2 Hf1 Hf1 74.20(7) 27_557 29_557 ?
Hf1 Hf1 Hf1 60.0 2_665 29_557 ?
O1 Hf1 Hf1 89.43(15) . 26_467 ?
O1 Hf1 Hf1 89.43(15) 27_557 26_467 ?
O1 Hf1 Hf1 34.94(9) 4_465 26_467 ?
O1 Hf1 Hf1 34.94(9) 26_467 26_467 ?
O2 Hf1 Hf1 110.18(5) . 26_467 ?
O2 Hf1 Hf1 74.20(7) 8_456 26_467 ?
O2 Hf1 Hf1 164.20(7) 10_656 26_467 ?
O2 Hf1 Hf1 110.18(5) 27_557 26_467 ?
Hf1 Hf1 Hf1 90.0 2_665 26_467 ?
Hf1 Hf1 Hf1 60.0 29_557 26_467 ?
O1 Hf1 Hf1 34.94(9) . 5_575 ?
O1 Hf1 Hf1 89.43(15) 27_557 5_575 ?
O1 Hf1 Hf1 34.94(9) 4_465 5_575 ?
O1 Hf1 Hf1 89.43(15) 26_467 5_575 ?
O2 Hf1 Hf1 74.20(7) . 5_575 ?
O2 Hf1 Hf1 110.18(5) 8_456 5_575 ?
O2 Hf1 Hf1 110.18(5) 10_656 5_575 ?
O2 Hf1 Hf1 164.20(7) 27_557 5_575 ?
Hf1 Hf1 Hf1 60.0 2_665 5_575 ?
Hf1 Hf1 Hf1 90.0 29_557 5_575 ?
Hf1 Hf1 Hf1 60.0 26_467 5_575 ?
C1 O2 Hf1 132.2(2) . . ?
Hf1 O1 Hf1 110.12(17) 2_665 5_575 ?
Hf1 O1 Hf1 110.12(17) 2_665 . ?
Hf1 O1 Hf1 110.12(17) 5_575 . ?
N1 C11 C10 127.3(6) . . ?
N1 C11 C12 111.4(6) . . ?
C10 C11 C12 121.3(6) . . ?
O2 C1 O2 127.3(4) 21 . ?
O2 C1 C2 116.4(2) 21 . ?
O2 C1 C2 116.4(2) . . ?
C3 C2 C3 118.2(6) . 21 ?
C3 C2 C1 120.9(3) . . ?
C3 C2 C1 120.9(3) 21 . ?
C2 C3 C4 120.5(6) . . ?
C2 C3 H3 119.8 . . ?
C4 C3 H3 119.8 . . ?
C5 C4 C3 121.7(6) . . ?
C5 C4 H4 119.2 . . ?
C3 C4 H4 119.2 . . ?
C11 N1 C11 105.0(7) . 3_565 ?
C11 N1 Cu1 127.5(4) . . ?
C11 N1 Cu1 127.5(4) 3_565 . ?
C4 C5 C4 117.5(8) 21 . ?
C4 C5 C6 121.2(4) 21 . ?
C4 C5 C6 121.3(4) . . ?
C7 C6 C7 57.2(11) 21 30 ?
C7 C6 C7 90.5(14) 21 46 ?
C7 C6 C7 117.8(11) 30 46 ?
C7 C6 C7 117.8(11) 21 . ?
C7 C6 C7 90.5(14) 30 . ?
C7 C6 C7 57.2(11) 46 . ?
C7 C6 C5 121.1(6) 21 . ?
C7 C6 C5 121.1(6) 30 . ?
C7 C6 C5 121.1(6) 46 . ?
C7 C6 C5 121.1(6) . . ?
C8 C9 C8 53.4(12) 30 21 ?
C8 C9 C8 97.4(15) 30 . ?
C8 C9 C8 122.1(13) 21 . ?
C8 C9 C8 122.1(13) 30 46 ?
C8 C9 C8 97.4(15) 21 46 ?
C8 C9 C8 53.4(12) . 46 ?
C8 C9 C10 118.9(6) 30 . ?
C8 C9 C10 118.9(6) 21 . ?
C8 C9 C10 118.9(6) . . ?
C8 C9 C10 118.9(6) 46 . ?
C9 C8 C7 117.7(16) . . ?
C9 C8 H8 121.1 . . ?
C7 C8 H8 121.1 . . ?
N1 Cu1 N1 180.0 29_556 5_565 ?
N1 Cu1 N1 90.0 29_556 25_566 ?
N1 Cu1 N1 90.0 5_565 25_566 ?
N1 Cu1 N1 90.0 29_556 . ?
N1 Cu1 N1 90.0 5_565 . ?
N1 Cu1 N1 180.0 25_566 . ?
C11 C10 C11 120.4(8) . 21 ?
C11 C10 C9 119.8(4) . . ?
C11 C10 C9 119.8(4) 21 . ?
C12 C12 C11 106.1(4) 3_565 . ?
C12 C12 H12 127.0 3_565 . ?
C11 C12 H12 127.0 . . ?
C6 C7 C8 122.1(14) . . ?
C6 C7 C8 94.5(9) . 46 ?
C8 C7 C8 40.9(7) . 46 ?
C6 C7 C7 44.8(7) . 30 ?
C8 C7 C7 92.3(13) . 30 ?
C8 C7 C7 91.7(10) 46 30 ?
C6 C7 H7 119.0 . . ?
C8 C7 H7 119.0 . . ?
C8 C7 H7 134.4 46 . ?
C7 C7 H7 133.7 30 . ?

_refine_diff_density_max         1.136
_refine_diff_density_min         -2.200
_refine_diff_density_rms         0.089

_shelxl_version_number           2013-4

# start Validation Reply Form
_vrf_PLAT213_1                   
;                                                                         
PROBLEM: Atom Cu1             has ADP max/min Ratio .....        4.8 prolat
          Atom C3              has ADP max/min Ratio .....        4.4 prolat
          Atom C4              has ADP max/min Ratio .....        4.9 prolat
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. 
;
_vrf_PLAT215_1                   
;
PROBLEM:  Disordered C7        has ADP max/min Ratio .....        4.1 
          Disordered C8        has ADP max/min Ratio .....        4.6    
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, C7 and C8 have large ADP max/min Ratio.
;
_vrf_PLAT220_1                   
;
PROBLEM:  Large Non-Solvent  C     Ueq(max)/Ueq(min) Range        6.5 Ratio 
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, some C atoms such as C7 have large  
Ueq(max)/Ueq(min) Range.
;
_vrf_PLAT241_1                   
;
PROBLEM: High      Ueq as Compared to Neighbors for .....         C4 Check 
         High      Ueq as Compared to Neighbors for .....        C10 Check 
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, C4 and C10 have high Ueq.
;
_vrf_PLAT242_1                   
;
PROBLEM: Low       Ueq as Compared to Neighbors for .....         C9 Check  
         
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. 
;
_vrf_PLAT250_1                   
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        8.3 Note  
RESPONSE: Though we tried our best, the final data is not high quality due 
to the high porosity. Thus, the diffraction of the crystal is still weak.
;
# end Validation Reply Form

