# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 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_w_a_sq
_database_code_depnum_ccdc_archive 'CCDC 2205590'
loop_
_audit_author_name
_audit_author_address
'LIngyao Wang'
;Zhejiang Normal University
China
;
_audit_update_record             
;
2022-09-06 deposited with the CCDC.	2022-11-18 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C24 H20 Cu F6 N4 Ti'
_chemical_formula_weight         589.88

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0137 0.0067 '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 -2.7974 3.6876 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0583 0.0400 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0241 0.0134 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.3343 1.4243 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      tetragonal
_space_group_IT_number           85
_space_group_name_H-M_alt        'P 4/n'
_space_group_name_Hall           '-P 4a'

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

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y+1/2, z'
'-y+1/2, x, z'
'y, -x+1/2, z'
'-x, -y, -z'
'x-1/2, y-1/2, -z'
'y-1/2, -x, -z'
'-y, x-1/2, -z'

_cell_length_a                   18.8668(15)
_cell_length_b                   18.8668(15)
_cell_length_c                   8.3590(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2975.4(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    193(2)
_cell_measurement_reflns_used    4120
_cell_measurement_theta_min      4.08
_cell_measurement_theta_max      49.09

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.658
_exptl_crystal_F_000             594
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    2.866
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      193(2)
_diffrn_radiation_wavelength     1.34139
_diffrn_radiation_type           GaK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            18340
_diffrn_reflns_av_unetI/netI     0.0870
_diffrn_reflns_av_R_equivalents  0.0899
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         2.882
_diffrn_reflns_theta_max         63.489
_diffrn_reflns_theta_full        53.594
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3651
_reflns_number_gt                1528
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_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)+(0.1000P)²+0.2500P] 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         3651
_refine_ls_number_parameters     132
_refine_ls_number_restraints     72
_refine_ls_R_factor_all          0.1621
_refine_ls_R_factor_gt           0.1133
_refine_ls_wR_factor_ref         0.3467
_refine_ls_wR_factor_gt          0.3229
_refine_ls_goodness_of_fit_ref   1.451
_refine_ls_restrained_S_all      1.468
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001

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
C1 C 0.4284(4) 0.4282(4) 0.4476(7) 0.1135(19) Uani 1 1 d . U . . .
C2 C 0.4846(4) 0.4846(4) 0.4425(8) 0.156(3) Uani 1 1 d . U . . .
H2 H 0.498922 0.499211 0.338629 0.187 Uiso 1 1 calc R U . . .
Cu1 Cu 0.250000 0.250000 0.44395(14) 0.0782(6) Uani 1 4 d S T P A .
F1 F 0.250000 0.250000 0.7277(7) 0.0998(17) Uani 1 4 d S T P A .
F3 F 0.250000 0.250000 1.1712(5) 0.0731(13) Uani 1 4 d S T P A .
F2 F 0.3180(11) 0.3147(12) 0.9514(9) 0.131(10) Uani 0.38(2) 1 d . U P A 1
C3 C 0.4286(8) 0.3775(8) 0.3291(15) 0.120(5) Uani 0.509(9) 1 d . U P B 1
H3 H 0.466729 0.373196 0.255466 0.145 Uiso 0.509(9) 1 calc R U P B 1
C4 C 0.3698(7) 0.3328(7) 0.3230(13) 0.095(4) Uani 0.509(9) 1 d . U P B 1
H4 H 0.361406 0.306512 0.228010 0.113 Uiso 0.509(9) 1 calc R U P B 1
C5 C 0.3855(8) 0.4193(7) 0.5653(14) 0.099(4) Uani 0.509(9) 1 d . U P B 1
H5 H 0.391714 0.447450 0.658430 0.119 Uiso 0.509(9) 1 calc R U P B 1
C6 C 0.3329(8) 0.3726(7) 0.5627(12) 0.096(4) Uani 0.509(9) 1 d . U P B 1
H6 H 0.299438 0.372137 0.647557 0.115 Uiso 0.509(9) 1 calc R U P B 1
F2' F 0.2511(10) 0.3465(3) 0.9455(7) 0.147(6) Uani 0.62(2) 1 d . U P A 2
C3' C 0.3776(7) 0.4297(7) 0.3271(15) 0.111(4) Uani 0.491(9) 1 d . U P B 2
H3' H 0.374102 0.467493 0.252349 0.133 Uiso 0.491(9) 1 calc R U P B 2
C4' C 0.3322(7) 0.3716(7) 0.3249(13) 0.087(3) Uani 0.491(9) 1 d . U P B 2
H4' H 0.303711 0.364661 0.232484 0.104 Uiso 0.491(9) 1 calc R U P B 2
C5' C 0.4213(8) 0.3837(8) 0.5664(14) 0.098(4) Uani 0.491(9) 1 d . U P B 2
H5' H 0.450821 0.388627 0.657770 0.117 Uiso 0.491(9) 1 calc R U P B 2
C6' C 0.3723(7) 0.3304(8) 0.5622(13) 0.098(4) Uani 0.491(9) 1 d . U P B 2
H6' H 0.371072 0.296376 0.645916 0.117 Uiso 0.491(9) 1 calc R U P B 2
N1 N 0.3263(3) 0.3258(3) 0.4415(5) 0.0929(13) Uani 1 1 d . . . . .
Ti1 Ti 0.250000 0.250000 0.94559(19) 0.0920(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
C1 C5 1.285(13) . ?
C1 C5' 1.307(14) . ?
C1 C3 1.377(14) . ?
C1 C3' 1.390(14) . ?
C1 C2 1.504(9) . ?
C2 C2 1.264(12) 5_666 ?
C2 H2 0.9500 . ?
Cu1 N1 2.029(5) 2 ?
Cu1 N1 2.029(5) 4 ?
Cu1 N1 2.029(5) 3 ?
Cu1 N1 2.029(5) . ?
Cu1 F3 2.280(4) 1_554 ?
Cu1 F1 2.372(6) . ?
F1 Ti1 1.822(6) . ?
F3 Ti1 1.886(5) . ?
F2 Ti1 1.771(11) . ?
C3 C4 1.393(16) . ?
C3 H3 0.9500 . ?
C4 N1 1.294(11) . ?
C4 H4 0.9500 . ?
C5 C6 1.326(15) . ?
C5 H5 0.9500 . ?
C6 N1 1.350(12) . ?
C6 H6 0.9500 . ?
F2' Ti1 1.822(6) . ?
C3' C4' 1.392(15) . ?
C3' H3' 0.9500 . ?
C4' N1 1.307(12) . ?
C4' H4' 0.9500 . ?
C5' C6' 1.366(17) . ?
C5' H5' 0.9500 . ?
C6' N1 1.334(13) . ?
C6' H6' 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
C5 C1 C3 117.5(10) . . ?
C5' C1 C3' 119.6(10) . . ?
C5 C1 C2 123.9(8) . . ?
C5' C1 C2 123.2(8) . . ?
C3 C1 C2 118.0(8) . . ?
C3' C1 C2 116.8(8) . . ?
C2 C2 C1 128.9(9) 5_666 . ?
C2 C2 H2 115.6 5_666 . ?
C1 C2 H2 115.6 . . ?
N1 Cu1 N1 89.994(3) 2 4 ?
N1 Cu1 N1 89.994(3) 2 3 ?
N1 Cu1 N1 178.8(2) 4 3 ?
N1 Cu1 N1 178.8(2) 2 . ?
N1 Cu1 N1 89.993(3) 4 . ?
N1 Cu1 N1 89.996(3) 3 . ?
N1 Cu1 F3 89.42(12) 2 1_554 ?
N1 Cu1 F3 89.42(12) 4 1_554 ?
N1 Cu1 F3 89.42(12) 3 1_554 ?
N1 Cu1 F3 89.42(12) . 1_554 ?
N1 Cu1 F1 90.58(12) 2 . ?
N1 Cu1 F1 90.58(12) 4 . ?
N1 Cu1 F1 90.58(12) 3 . ?
N1 Cu1 F1 90.58(12) . . ?
F3 Cu1 F1 180.0 1_554 . ?
Ti1 F1 Cu1 180.0 . . ?
Ti1 F3 Cu1 180.0 . 1_556 ?
C4 C3 C1 116.3(11) . . ?
C4 C3 H3 121.8 . . ?
C1 C3 H3 121.8 . . ?
N1 C4 C3 122.7(10) . . ?
N1 C4 H4 118.7 . . ?
C3 C4 H4 118.7 . . ?
C1 C5 C6 123.0(11) . . ?
C1 C5 H5 118.5 . . ?
C6 C5 H5 118.5 . . ?
N1 C6 C5 121.1(10) . . ?
N1 C6 H6 119.5 . . ?
C5 C6 H6 119.5 . . ?
C4' C3' C1 114.6(11) . . ?
C4' C3' H3' 122.7 . . ?
C1 C3' H3' 122.7 . . ?
N1 C4' C3' 124.3(10) . . ?
N1 C4' H4' 117.9 . . ?
C3' C4' H4' 117.9 . . ?
C1 C5' C6' 121.5(11) . . ?
C1 C5' H5' 119.3 . . ?
C6' C5' H5' 119.3 . . ?
N1 C6' C5' 120.5(11) . . ?
N1 C6' H6' 119.8 . . ?
C5' C6' H6' 119.8 . . ?
C4 N1 C6 116.6(8) . . ?
C6' N1 C4' 117.7(9) . . ?
C4 N1 Cu1 122.0(6) . . ?
C6' N1 Cu1 120.0(6) . . ?
C6 N1 Cu1 121.3(6) . . ?
C4' N1 Cu1 122.3(6) . . ?
F2 Ti1 F2 89.957(14) 2 4 ?
F2 Ti1 F2 89.957(15) 2 3 ?
F2 Ti1 F2 176.9(5) 4 3 ?
F2 Ti1 F2 176.9(5) 2 . ?
F2 Ti1 F2 89.959(17) 4 . ?
F2 Ti1 F2 89.956(16) 3 . ?
F2 Ti1 F1 91.6(2) 2 . ?
F2 Ti1 F1 91.6(2) 4 . ?
F2 Ti1 F1 91.6(2) 3 . ?
F2 Ti1 F1 91.6(2) . . ?
F1 Ti1 F2' 89.96(18) . . ?
F2 Ti1 F2' 45.8(5) 2 2 ?
F2 Ti1 F2' 44.2(5) 4 2 ?
F2 Ti1 F2' 135.8(5) 3 2 ?
F2 Ti1 F2' 134.2(5) . 2 ?
F1 Ti1 F2' 89.96(18) . 2 ?
F2' Ti1 F2' 179.9(4) . 2 ?
F2 Ti1 F2' 135.8(5) 2 4 ?
F2 Ti1 F2' 45.8(5) 4 4 ?
F2 Ti1 F2' 134.2(5) 3 4 ?
F2 Ti1 F2' 44.2(5) . 4 ?
F1 Ti1 F2' 89.96(18) . 4 ?
F2 Ti1 F2' 44.2(5) 2 3 ?
F2 Ti1 F2' 134.2(5) 4 3 ?
F2 Ti1 F2' 45.8(5) 3 3 ?
F2 Ti1 F2' 135.8(5) . 3 ?
F1 Ti1 F2' 89.96(18) . 3 ?
F2' Ti1 F2' 89.999(2) . 3 ?
F2' Ti1 F2' 90.000(3) 2 3 ?
F2' Ti1 F2' 179.9(4) 4 3 ?
F2 Ti1 F3 88.4(2) 2 . ?
F2 Ti1 F3 88.4(2) 4 . ?
F2 Ti1 F3 88.4(2) 3 . ?
F2 Ti1 F3 88.4(2) . . ?
F1 Ti1 F3 180.0 . . ?
F2' Ti1 F3 90.04(18) . . ?
F2' Ti1 F3 90.04(18) 2 . ?
F2' Ti1 F3 90.04(18) 4 . ?
F2' Ti1 F3 90.04(18) 3 . ?

_refine_diff_density_max         0.596
_refine_diff_density_min         -0.521
_refine_diff_density_rms         0.078



