# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# 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_SUM-1Hf
_database_code_depnum_ccdc_archive 'CCDC 2121494'
loop_
_audit_author_name
_audit_author_address
'Chong Liu'
;Sichuan University
China
;
_audit_update_record             
;
2021-12-08 deposited with the CCDC.	2022-01-26 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT213_SUM-1Hf             
;
PROBLEM: Atom Hf              has ADP max/min Ratio .....        4.9 prolat
RESPONSE: The high ADP max/min ratio of Hf is due to dynamic disorder or thermal motion.
;
# Added during the CSD deposition process: Wednesday 08 December 2021 08:09 AM
# end Validation Reply Form

_audit_creation_date             2021-11-11
_audit_creation_method           
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6405)
;
_shelxl_version_number           2014/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.33(C48 H36 Hf3 N12 O24)'
_chemical_formula_sum            'C16 H12 Hf N4 O8'
_chemical_formula_weight         566.79
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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'
Hf Hf -0.5830 6.1852 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      hexagonal
_space_group_IT_number           191
_space_group_name_H-M_alt        'P 6/m m m'
_space_group_name_Hall           '-P 6 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, z'
'y, -x+y, z'
'x-y, x, z'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -z'
'-y, -x, -z'
'-x+y, y, -z'
'x, x-y, -z'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'x, y, -z'
'-y, x-y, -z'
'-x+y, -x, -z'
'-y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'y, x, z'
'x-y, -y, z'
'-x, -x+y, z'

_cell_length_a                   23.1152(8)
_cell_length_b                   23.1152(8)
_cell_length_c                   8.1157(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     3755.4(3)
_cell_formula_units_Z            3
_cell_measurement_reflns_used    5916
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      25.319
_cell_measurement_theta_min      2.510
_shelx_estimated_absorpt_T_max   0.959
_shelx_estimated_absorpt_T_min   0.850
_exptl_absorpt_coefficient_mu    2.103
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5862
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0979 before and 0.0784 after correction.
The Ratio of minimum to maximum transmission is 0.7862.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.752
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1241
_diffrn_reflns_av_unetI/netI     0.0385
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            33357
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.495
_diffrn_reflns_theta_min         2.035
_diffrn_ambient_temperature      150.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1507
_reflns_number_total             1723
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         1.591
_refine_diff_density_min         -4.466
_refine_diff_density_rms         0.200
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     64
_refine_ls_number_reflns         1723
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0618
_refine_ls_R_factor_gt           0.0562
_refine_ls_restrained_S_all      1.058
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1054P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1386
_refine_ls_wR_factor_ref         0.1413
_refine_special_details          ?
_olex2_refinement_description    
;
1. Others
 Fixed Sof: O2(0.5) O1(0.5) N1(0.5) H1(0.5) C3(0.5) H3(0.5) C4(0.5) H4(0.5)
 C1(0.5)
2.a Ternary CH refined with riding coordinates:
 N1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
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
Hf Hf 1.0000 0.5000 1.0000 0.0306(2) Uani 1 8 d S T P A .
C2 C 0.8180(4) 0.2989(5) 1.0000 0.065(2) Uani 1 2 d S T P . .
O2 O 0.9167(4) 0.4032(4) 0.9334(9) 0.053(2) Uani 0.5 1 d . . . . .
O1 O 0.9633(3) 0.4394(4) 0.7808(9) 0.0484(18) Uani 0.5 1 d . . . A .
N1 N 0.9051(4) 0.3809(5) 0.7992(11) 0.051(2) Uani 0.5 1 d . . . A .
H1 H 0.8740 0.3973 0.7659 0.061 Uiso 0.5 1 calc R . . . .
C3 C 0.7711(6) 0.2878(6) 0.8838(15) 0.061(3) Uani 0.5 1 d . . . A 1
H3 H 0.7795 0.3209 0.8032 0.073 Uiso 0.5 1 calc R . . A 1
C4 C 0.8066(8) 0.2519(8) 0.8852(16) 0.094(5) Uani 0.5 1 d . . . A 2
H4 H 0.8397 0.2600 0.8048 0.113 Uiso 0.5 1 calc R . . A 2
C1 C 0.8837(6) 0.3635(6) 0.9481(11) 0.040(2) Uani 0.5 1 d . . . A .


_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
Hf O2 2.168(8) 13_767 ?
Hf O2 2.167(8) . ?
Hf O2 2.168(8) 4_765 ?
Hf O2 2.168(8) 16_557 ?
Hf O1 2.158(7) 24_765 ?
Hf O1 2.158(7) 9_767 ?
Hf O1 2.158(7) 21 ?
Hf O1 2.158(7) 16_557 ?
Hf O1 2.158(7) 12_557 ?
Hf O1 2.158(7) 13_767 ?
Hf O1 2.158(7) 4_765 ?
Hf O1 2.158(7) . ?
C2 C3 1.360(14) 16_557 ?
C2 C3 1.360(14) . ?
C2 C4 1.353(15) 16_557 ?
C2 C4 1.353(15) . ?
C2 C1 1.563(14) . ?
C2 C1 1.563(14) 16_557 ?
O2 O2 1.081(15) 16_557 ?
O2 O1 1.579(10) . ?
O2 N1 1.176(11) . ?
O2 C1 0.860(12) . ?
O2 C1 1.285(10) 16_557 ?
O1 O1 1.469(12) 24_765 ?
O1 N1 1.357(10) . ?
N1 C1 1.291(13) . ?
C3 C3 1.36(2) 19_665 ?
C4 C4 1.35(3) 19_665 ?
C1 O2 1.285(10) 16_557 ?
C1 C1 0.842(17) 16_557 ?

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 Hf O2 180.0 . 13_767 ?
O2 Hf O2 180.0 16_557 4_765 ?
O2 Hf O2 151.1(4) . 4_765 ?
O2 Hf O2 151.1(4) 13_767 16_557 ?
O2 Hf O2 28.9(4) . 16_557 ?
O2 Hf O2 28.9(4) 13_767 4_765 ?
O1 Hf O2 101.6(3) 9_767 . ?
O1 Hf O2 101.6(3) 24_765 16_557 ?
O1 Hf O2 71.2(3) 13_767 4_765 ?
O1 Hf O2 102.1(3) 9_767 4_765 ?
O1 Hf O2 42.8(3) 16_557 16_557 ?
O1 Hf O2 102.1(3) 21 16_557 ?
O1 Hf O2 108.8(3) . 4_765 ?
O1 Hf O2 71.2(3) 16_557 . ?
O1 Hf O2 101.6(3) 12_557 4_765 ?
O1 Hf O2 78.4(3) 12_557 16_557 ?
O1 Hf O2 71.2(3) . 16_557 ?
O1 Hf O2 78.4(3) 24_765 4_765 ?
O1 Hf O2 102.1(3) 24_765 13_767 ?
O1 Hf O2 108.8(3) 4_765 . ?
O1 Hf O2 77.9(3) 12_557 13_767 ?
O1 Hf O2 77.9(3) 24_765 . ?
O1 Hf O2 108.8(3) 16_557 13_767 ?
O1 Hf O2 137.2(3) . 13_767 ?
O1 Hf O2 71.2(3) 4_765 13_767 ?
O1 Hf O2 102.1(3) 12_557 . ?
O1 Hf O2 42.8(3) . . ?
O1 Hf O2 42.8(3) 13_767 13_767 ?
O1 Hf O2 137.2(3) 13_767 . ?
O1 Hf O2 137.2(3) 4_765 16_557 ?
O1 Hf O2 78.4(3) 21 . ?
O1 Hf O2 101.6(3) 21 13_767 ?
O1 Hf O2 77.9(3) 9_767 16_557 ?
O1 Hf O2 77.9(3) 21 4_765 ?
O1 Hf O2 108.8(3) 13_767 16_557 ?
O1 Hf O2 78.4(3) 9_767 13_767 ?
O1 Hf O2 137.2(3) 16_557 4_765 ?
O1 Hf O2 42.8(3) 4_765 4_765 ?
O1 Hf O1 140.2(3) . 12_557 ?
O1 Hf O1 180.0(4) 16_557 4_765 ?
O1 Hf O1 111.0(4) 13_767 4_765 ?
O1 Hf O1 126.2(5) 12_557 4_765 ?
O1 Hf O1 53.8(5) 12_557 16_557 ?
O1 Hf O1 39.8(3) . 24_765 ?
O1 Hf O1 111.0(4) 9_767 24_765 ?
O1 Hf O1 39.8(3) 13_767 12_557 ?
O1 Hf O1 126.2(5) 24_765 16_557 ?
O1 Hf O1 126.2(5) 13_767 21 ?
O1 Hf O1 69.0(4) . 4_765 ?
O1 Hf O1 111.0(4) 21 12_557 ?
O1 Hf O1 53.8(5) 24_765 4_765 ?
O1 Hf O1 140.2(3) 9_767 4_765 ?
O1 Hf O1 140.2(3) 21 16_557 ?
O1 Hf O1 69.0(4) 9_767 12_557 ?
O1 Hf O1 39.8(3) 9_767 16_557 ?
O1 Hf O1 180.0 . 13_767 ?
O1 Hf O1 126.2(5) . 9_767 ?
O1 Hf O1 180.0 24_765 12_557 ?
O1 Hf O1 180.0 21 9_767 ?
O1 Hf O1 53.8(5) 13_767 9_767 ?
O1 Hf O1 140.2(3) 13_767 24_765 ?
O1 Hf O1 111.0(4) . 16_557 ?
O1 Hf O1 39.8(3) 21 4_765 ?
O1 Hf O1 69.0(4) 21 24_765 ?
O1 Hf O1 69.0(4) 13_767 16_557 ?
O1 Hf O1 53.8(5) . 21 ?
C3 C2 C3 87.8(12) . 16_557 ?
C3 C2 C1 107.1(7) 16_557 16_557 ?
C3 C2 C1 132.0(9) 16_557 . ?
C3 C2 C1 132.0(9) . 16_557 ?
C3 C2 C1 107.1(7) . . ?
C4 C2 C4 87.0(13) . 16_557 ?
C4 C2 C1 131.1(9) . 16_557 ?
C4 C2 C1 106.7(8) . . ?
C4 C2 C1 131.1(9) 16_557 . ?
C4 C2 C1 106.7(8) 16_557 16_557 ?
C1 C2 C1 31.3(7) . 16_557 ?
O2 O2 Hf 75.6(2) 16_557 . ?
O2 O2 O1 141.7(4) 16_557 . ?
O2 O2 N1 157.7(6) 16_557 . ?
O2 O2 C1 41.5(5) 16_557 16_557 ?
O1 O2 Hf 68.3(4) . . ?
N1 O2 Hf 125.0(7) . . ?
N1 O2 O1 56.8(5) . . ?
N1 O2 C1 117.1(8) . 16_557 ?
C1 O2 Hf 157.5(10) . . ?
C1 O2 Hf 117.1(6) 16_557 . ?
C1 O2 O2 82.0(8) . 16_557 ?
C1 O2 O1 133.0(10) . . ?
C1 O2 O1 166.1(9) 16_557 . ?
C1 O2 N1 77.0(10) . . ?
C1 O2 C1 40.5(10) . 16_557 ?
O2 O1 Hf 68.9(4) . . ?
O1 O1 Hf 70.11(16) 24_765 . ?
O1 O1 O2 126.2(4) 24_765 . ?
N1 O1 Hf 115.3(5) . . ?
N1 O1 O2 46.5(5) . . ?
N1 O1 O1 149.2(6) . 24_765 ?
O2 N1 O1 76.7(7) . . ?
O2 N1 C1 40.5(6) . . ?
C1 N1 O1 116.7(9) . . ?
C2 C3 C3 119.5(6) . 19_665 ?
C2 C4 C4 119.9(7) . 19_665 ?
O2 C1 C2 167.7(13) . . ?
O2 C1 C2 115.3(7) 16_557 . ?
O2 C1 O2 56.5(10) . 16_557 ?
O2 C1 N1 118.6(10) 16_557 . ?
O2 C1 N1 62.6(9) . . ?
N1 C1 C2 126.0(8) . . ?
C1 C1 C2 74.4(3) 16_557 . ?
C1 C1 O2 98.0(8) 16_557 . ?
C1 C1 O2 41.5(5) 16_557 16_557 ?
C1 C1 N1 159.3(6) 16_557 . ?

_smtbx_masks_special_details     ?
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 -0.510 0.385 -0.344 2349.4 630.5 ?


_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# 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_SUM-1Zr
_database_code_depnum_ccdc_archive 'CCDC 2121493'
loop_
_audit_author_name
_audit_author_address
'Chong Liu'
;Sichuan University
China
;
_audit_update_record             
;
2021-12-08 deposited with the CCDC.	2022-01-26 downloaded from the CCDC.
;
_audit_creation_date             2021-07-26
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelxl_version_number           2014/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.33(C48 H36 N12 O24 Zr3)'
_chemical_formula_sum            'C16 H12 N4 O8 Zr'
_chemical_formula_weight         479.52
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zr Zr -2.9673 0.5597 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      hexagonal
_space_group_IT_number           191
_space_group_name_H-M_alt        'P 6/m m m'
_space_group_name_Hall           '-P 6 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, z'
'y, -x+y, z'
'x-y, x, z'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -z'
'-y, -x, -z'
'-x+y, y, -z'
'x, x-y, -z'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'x, y, -z'
'-y, x-y, -z'
'-x+y, -x, -z'
'-y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'y, x, z'
'x-y, -y, z'
'-x, -x+y, z'

_cell_length_a                   23.168(2)
_cell_length_b                   23.168(2)
_cell_length_c                   8.0801(11)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     3756.1(9)
_cell_formula_units_Z            3
_cell_measurement_reflns_used    4098
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      23.40
_cell_measurement_theta_min      2.69
_shelx_estimated_absorpt_T_max   0.979
_shelx_estimated_absorpt_T_min   0.974
_exptl_absorpt_coefficient_mu    0.240
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5888
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1032 before and 0.0853 after correction. The Ratio of minimum to maximum transmission is 0.7897. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.636
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1500
_diffrn_reflns_av_unetI/netI     0.0507
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            36009
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.496
_diffrn_reflns_theta_min         2.030
_diffrn_ambient_temperature      120.0
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1315
_reflns_number_total             1724
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         1.664
_refine_diff_density_min         -1.374
_refine_diff_density_rms         0.128
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     64
_refine_ls_number_reflns         1724
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1019
_refine_ls_R_factor_gt           0.0892
_refine_ls_restrained_S_all      1.080
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1742P)²+2.6618P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2487
_refine_ls_wR_factor_ref         0.2633
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2. Others
 Fixed Sof: O2(0.5) O1(0.5) N1(0.5) H1(0.5) C3(0.5) H3(0.5) C4(0.5) H4(0.5)
 C1(0.5)
3.a Ternary CH refined with riding coordinates:
 N1(H1)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
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 1.0000 0.5000 1.0000 0.0341(4) Uani 1 8 d S T P A .
C2 C 0.8196(3) 0.2982(3) 1.0000 0.0596(17) Uani 1 2 d S T P . .
O2 O 0.9149(3) 0.4012(3) 0.9336(7) 0.0410(12) Uani 0.5 1 d . . . . .
O1 O 0.9636(2) 0.4394(3) 0.7800(7) 0.0465(14) Uani 0.5 1 d . . . A .
N1 N 0.9051(3) 0.3794(3) 0.7977(9) 0.0477(16) Uani 0.5 1 d . . . A .
H1 H 0.8741 0.3955 0.7631 0.057 Uiso 0.5 1 calc R . . . .
C3 C 0.7730(5) 0.2865(4) 0.8861(12) 0.059(2) Uani 0.5 1 d . . . A 1
H3 H 0.7809 0.3193 0.8050 0.071 Uiso 0.5 1 calc R . . A 1
C4 C 0.8084(6) 0.2509(6) 0.8906(13) 0.082(3) Uani 0.5 1 d . . . A 2
H4 H 0.8417 0.2582 0.8115 0.099 Uiso 0.5 1 calc R . . A 2
C1 C 0.8827(4) 0.3625(4) 0.9477(9) 0.0424(17) Uani 0.5 1 d . . . A .


_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 2.214(5) 13_767 ?
Zr1 O2 2.214(5) 16_557 ?
Zr1 O2 2.214(5) 4_765 ?
Zr1 O2 2.214(5) . ?
Zr1 O1 2.158(5) 12_557 ?
Zr1 O1 2.158(5) 13_767 ?
Zr1 O1 2.158(5) 9_767 ?
Zr1 O1 2.158(5) 16_557 ?
Zr1 O1 2.158(5) 24_765 ?
Zr1 O1 2.158(5) 4_765 ?
Zr1 O1 2.158(5) . ?
Zr1 O1 2.158(5) 21 ?
C2 C3 1.340(11) 16_557 ?
C2 C3 1.340(11) . ?
C2 C4 1.327(12) 16_557 ?
C2 C4 1.327(12) . ?
C2 C1 1.536(10) 16_557 ?
C2 C1 1.536(10) . ?
O2 O2 1.074(11) 16_557 ?
O2 O1 1.611(7) . ?
O2 N1 1.182(8) . ?
O2 C1 0.839(8) . ?
O2 C1 1.270(8) 16_557 ?
O1 O1 1.461(8) 24_765 ?
O1 N1 1.381(7) . ?
N1 H1 1.0000 . ?
N1 C1 1.299(10) . ?
C3 C3 1.377(17) 19_665 ?
C3 H3 0.9500 . ?
C4 C4 1.38(2) 19_665 ?
C4 H4 0.9500 . ?
C1 O2 1.270(8) 16_557 ?
C1 C1 0.845(15) 16_557 ?

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 180.0 . 13_767 ?
O2 Zr1 O2 28.1(3) 13_767 4_765 ?
O2 Zr1 O2 151.9(3) . 4_765 ?
O2 Zr1 O2 28.1(3) . 16_557 ?
O2 Zr1 O2 180.0 4_765 16_557 ?
O2 Zr1 O2 151.9(3) 13_767 16_557 ?
O1 Zr1 O2 109.2(2) 4_765 . ?
O1 Zr1 O2 136.78(19) 16_557 4_765 ?
O1 Zr1 O2 101.1(2) 24_765 16_557 ?
O1 Zr1 O2 43.22(19) . . ?
O1 Zr1 O2 101.9(2) 12_557 . ?
O1 Zr1 O2 43.22(19) 13_767 13_767 ?
O1 Zr1 O2 70.8(2) 16_557 . ?
O1 Zr1 O2 101.1(2) 21 13_767 ?
O1 Zr1 O2 109.2(2) . 4_765 ?
O1 Zr1 O2 78.9(2) 9_767 13_767 ?
O1 Zr1 O2 101.9(2) 21 16_557 ?
O1 Zr1 O2 101.9(2) 24_765 13_767 ?
O1 Zr1 O2 136.78(19) 4_765 16_557 ?
O1 Zr1 O2 78.1(2) 12_557 13_767 ?
O1 Zr1 O2 101.1(2) 12_557 4_765 ?
O1 Zr1 O2 109.2(2) 16_557 13_767 ?
O1 Zr1 O2 43.22(19) 4_765 4_765 ?
O1 Zr1 O2 70.8(2) 4_765 13_767 ?
O1 Zr1 O2 78.1(2) 24_765 . ?
O1 Zr1 O2 136.78(19) . 13_767 ?
O1 Zr1 O2 109.2(2) 13_767 16_557 ?
O1 Zr1 O2 136.78(19) 13_767 . ?
O1 Zr1 O2 78.1(2) 9_767 16_557 ?
O1 Zr1 O2 78.9(2) 21 . ?
O1 Zr1 O2 43.22(19) 16_557 16_557 ?
O1 Zr1 O2 101.1(2) 9_767 . ?
O1 Zr1 O2 70.8(2) . 16_557 ?
O1 Zr1 O2 101.9(2) 9_767 4_765 ?
O1 Zr1 O2 78.9(2) 24_765 4_765 ?
O1 Zr1 O2 70.8(2) 13_767 4_765 ?
O1 Zr1 O2 78.1(2) 21 4_765 ?
O1 Zr1 O2 78.9(2) 12_557 16_557 ?
O1 Zr1 O1 69.1(3) 13_767 16_557 ?
O1 Zr1 O1 110.9(3) 16_557 . ?
O1 Zr1 O1 39.6(2) 13_767 12_557 ?
O1 Zr1 O1 140.4(2) 21 16_557 ?
O1 Zr1 O1 180.0 21 9_767 ?
O1 Zr1 O1 39.6(2) 9_767 16_557 ?
O1 Zr1 O1 39.6(2) 24_765 . ?
O1 Zr1 O1 125.9(3) 24_765 16_557 ?
O1 Zr1 O1 125.9(3) 13_767 21 ?
O1 Zr1 O1 54.1(3) 12_557 16_557 ?
O1 Zr1 O1 69.1(3) 21 24_765 ?
O1 Zr1 O1 110.9(3) 13_767 4_765 ?
O1 Zr1 O1 180.0 24_765 12_557 ?
O1 Zr1 O1 39.6(2) 21 4_765 ?
O1 Zr1 O1 140.4(2) 12_557 . ?
O1 Zr1 O1 140.4(2) 9_767 4_765 ?
O1 Zr1 O1 69.1(3) 4_765 . ?
O1 Zr1 O1 54.1(3) 24_765 4_765 ?
O1 Zr1 O1 54.1(3) 13_767 9_767 ?
O1 Zr1 O1 125.9(3) 12_557 4_765 ?
O1 Zr1 O1 140.4(2) 13_767 24_765 ?
O1 Zr1 O1 180.0(3) 16_557 4_765 ?
O1 Zr1 O1 110.9(3) 9_767 24_765 ?
O1 Zr1 O1 180.0 13_767 . ?
O1 Zr1 O1 69.1(3) 9_767 12_557 ?
O1 Zr1 O1 54.1(3) 21 . ?
O1 Zr1 O1 125.9(3) 9_767 . ?
O1 Zr1 O1 110.9(3) 21 12_557 ?
C3 C2 C3 86.8(9) . 16_557 ?
C3 C2 C1 131.7(6) 16_557 . ?
C3 C2 C1 106.7(5) 16_557 16_557 ?
C3 C2 C1 106.7(5) . . ?
C3 C2 C1 131.7(6) . 16_557 ?
C4 C2 C4 83.5(10) . 16_557 ?
C4 C2 C1 133.0(7) . 16_557 ?
C4 C2 C1 133.0(7) 16_557 . ?
C4 C2 C1 108.4(6) 16_557 16_557 ?
C4 C2 C1 108.4(6) . . ?
C1 C2 C1 31.9(6) . 16_557 ?
O2 O2 Zr1 75.97(15) 16_557 . ?
O2 O2 O1 140.4(3) 16_557 . ?
O2 O2 N1 158.2(4) 16_557 . ?
O2 O2 C1 40.9(4) 16_557 16_557 ?
O1 O2 Zr1 66.5(3) . . ?
N1 O2 Zr1 123.3(5) . . ?
N1 O2 O1 56.8(4) . . ?
N1 O2 C1 118.7(6) . 16_557 ?
C1 O2 Zr1 116.9(4) 16_557 . ?
C1 O2 Zr1 158.1(8) . . ?
C1 O2 O2 82.2(7) . 16_557 ?
C1 O2 O1 166.6(6) 16_557 . ?
C1 O2 O1 134.1(8) . . ?
C1 O2 N1 77.9(7) . . ?
C1 O2 C1 41.3(8) . 16_557 ?
O2 O1 Zr1 70.2(3) . . ?
O1 O1 Zr1 70.21(11) 24_765 . ?
O1 O1 O2 127.3(3) 24_765 . ?
N1 O1 Zr1 115.9(4) . . ?
N1 O1 O2 45.7(4) . . ?
N1 O1 O1 148.2(4) . 24_765 ?
O2 N1 O1 77.5(5) . . ?
O2 N1 H1 96.9 . . ?
O2 N1 C1 39.2(4) . . ?
O1 N1 H1 96.9 . . ?
C1 N1 O1 116.3(7) . . ?
C1 N1 H1 96.9 . . ?
C2 C3 C3 120.3(4) . 19_665 ?
C2 C3 H3 119.9 . . ?
C3 C3 H3 119.9 19_665 . ?
C2 C4 C4 120.7(5) . 19_665 ?
C2 C4 H4 119.7 . . ?
C4 C4 H4 119.7 19_665 . ?
O2 C1 C2 168.6(10) . . ?
O2 C1 C2 114.5(5) 16_557 . ?
O2 C1 O2 56.9(8) . 16_557 ?
O2 C1 N1 62.9(7) . . ?
O2 C1 N1 119.2(7) 16_557 . ?
O2 C1 C1 97.8(7) . 16_557 ?
N1 C1 C2 126.3(7) . . ?
C1 C1 C2 74.0(3) 16_557 . ?
C1 C1 O2 40.9(4) 16_557 16_557 ?
C1 C1 N1 158.9(5) 16_557 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Zr1 O2 O1 O1 43.4(2) . . . 24_765 ?
Zr1 O2 O1 N1 -178.0(6) . . . . ?
Zr1 O2 N1 O1 2.2(6) . . . . ?
Zr1 O2 N1 C1 174.1(9) . . . . ?
Zr1 O2 C1 C2 48(6) . . . . ?
Zr1 O2 C1 O2 4(2) . . . 16_557 ?
Zr1 O2 C1 N1 -167(2) . . . . ?
Zr1 O2 C1 C1 4(2) . . . 16_557 ?
Zr1 O1 N1 O2 -2.1(6) . . . . ?
Zr1 O1 N1 C1 -7.8(9) . . . . ?
O2 O2 O1 Zr1 -20.3(4) 16_557 . . . ?
O2 O2 O1 O1 23.2(6) 16_557 . . 24_765 ?
O2 O2 O1 N1 161.7(6) 16_557 . . . ?
O2 O2 N1 O1 -147.4(10) 16_557 . . . ?
O2 O2 N1 C1 24.6(11) 16_557 . . . ?
O2 O2 C1 C2 43(5) 16_557 . . . ?
O2 O2 C1 N1 -171.0(4) 16_557 . . . ?
O2 O2 C1 C1 0.001(4) 16_557 . . 16_557 ?
O2 O1 N1 C1 -5.7(6) . . . . ?
O2 N1 C1 C2 172.1(12) . . . . ?
O2 N1 C1 O2 -8.6(4) . . . 16_557 ?
O2 N1 C1 C1 -25.4(13) . . . 16_557 ?
O1 O2 N1 C1 171.9(8) . . . . ?
O1 O2 C1 C2 -155(4) . . . . ?
O1 O2 C1 O2 161.6(8) . . . 16_557 ?
O1 O2 C1 N1 -9.4(9) . . . . ?
O1 O2 C1 C1 161.6(8) . . . 16_557 ?
O1 O1 N1 O2 91.9(7) 24_765 . . . ?
O1 O1 N1 C1 86.3(9) 24_765 . . . ?
O1 N1 C1 C2 -179.1(7) . . . . ?
O1 N1 C1 O2 0.2(11) . . . 16_557 ?
O1 N1 C1 O2 8.8(9) . . . . ?
O1 N1 C1 C1 -16.6(18) . . . 16_557 ?
N1 O2 O1 Zr1 178.0(6) . . . . ?
N1 O2 O1 O1 -138.5(5) . . . 24_765 ?
N1 O2 C1 C2 -146(5) . . . . ?
N1 O2 C1 O2 171.0(4) . . . 16_557 ?
N1 O2 C1 C1 171.0(4) . . . 16_557 ?
C3 C2 C3 C3 -56.5(7) 16_557 . . 19_665 ?
C3 C2 C1 O2 0(5) 16_557 . . . ?
C3 C2 C1 O2 39.6(11) 16_557 . . 16_557 ?
C3 C2 C1 O2 140.5(7) . . . 16_557 ?
C3 C2 C1 O2 101(5) . . . . ?
C3 C2 C1 N1 -141.1(9) 16_557 . . . ?
C3 C2 C1 N1 -40.2(11) . . . . ?
C3 C2 C1 C1 146.3(6) . . . 16_557 ?
C3 C2 C1 C1 45.4(7) 16_557 . . 16_557 ?
C4 C2 C4 C4 58.1(8) 16_557 . . 19_665 ?
C4 C2 C1 O2 169(5) . . . . ?
C4 C2 C1 O2 -92(5) 16_557 . . . ?
C4 C2 C1 O2 -53.0(12) 16_557 . . 16_557 ?
C4 C2 C1 O2 -151.4(8) . . . 16_557 ?
C4 C2 C1 N1 27.9(11) . . . . ?
C4 C2 C1 N1 126.4(10) 16_557 . . . ?
C4 C2 C1 C1 -145.6(7) . . . 16_557 ?
C4 C2 C1 C1 -47.1(8) 16_557 . . 16_557 ?
C1 C2 C3 C3 -166.1(5) 16_557 . . 19_665 ?
C1 C2 C3 C3 170.7(4) . . . 19_665 ?
C1 C2 C4 C4 167.2(5) 16_557 . . 19_665 ?
C1 C2 C4 C4 -168.7(4) . . . 19_665 ?
C1 C2 C1 O2 -45(5) 16_557 . . . ?
C1 C2 C1 O2 -5.8(7) 16_557 . . 16_557 ?
C1 C2 C1 N1 173.5(7) 16_557 . . . ?
C1 O2 O1 Zr1 -108(2) 16_557 . . . ?
C1 O2 O1 Zr1 -171.0(11) . . . . ?
C1 O2 O1 O1 -64(2) 16_557 . . 24_765 ?
C1 O2 O1 O1 -127.5(10) . . . 24_765 ?
C1 O2 O1 N1 74(2) 16_557 . . . ?
C1 O2 O1 N1 11.0(11) . . . . ?
C1 O2 N1 O1 -165.2(7) 16_557 . . . ?
C1 O2 N1 O1 -171.9(8) . . . . ?
C1 O2 N1 C1 6.7(3) 16_557 . . . ?
C1 O2 C1 C2 43(5) 16_557 . . . ?
C1 O2 C1 O2 -0.001(6) 16_557 . . 16_557 ?
C1 O2 C1 N1 -171.0(4) 16_557 . . . ?

_smtbx_masks_special_details     ?
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 -0.340 -0.555 -0.712 2379.5 451.3 ?


_olex2_submission_special_instructions 'No special instructions were received'
