# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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_CuI_TTFTB
_database_code_depnum_ccdc_archive 'CCDC 2082445'
loop_
_audit_author_name
_audit_author_address
'Jian Su'
;Nanjing University
China
;
_audit_update_record             
;
2021-09-15 deposited with the CCDC.	2021-10-11 downloaded from the CCDC.
;
_audit_creation_date             2021-09-09
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         
'0.5(C68 H36 Cu2 O16 S8), C3 H7 N O, 2(C H4.5 N0.5)'
_chemical_formula_sum            'C39 H34 Cu N2 O9 S4'
_chemical_formula_weight         866.51
_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 0.0030 0.0020 '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 0.3200 1.2650 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0060 0.0030 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0110 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1250 0.1230 '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      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   19.1651(9)
_cell_length_b                   34.7043(16)
_cell_length_c                   8.8821(4)
_cell_angle_alpha                90
_cell_angle_beta                 97.5830(10)
_cell_angle_gamma                90
_cell_volume                     5855.9(5)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9977
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.58
_cell_measurement_theta_min      2.35
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.554
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    0.983
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       neddle-like
_exptl_crystal_F_000             1788
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0305
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            25669
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.604
_diffrn_reflns_theta_min         2.347
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.991
_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                   'fine-focus sealed tube'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5393
_reflns_number_total             6751
_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 v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.273
_refine_diff_density_min         -0.631
_refine_diff_density_rms         0.105
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         6751
_refine_ls_number_restraints     130
_refine_ls_R_factor_all          0.0739
_refine_ls_R_factor_gt           0.0616
_refine_ls_restrained_S_all      1.078
_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)+(0.1463P)²+7.6264P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2022
_refine_ls_wR_factor_ref         0.2154
_refine_special_details          
; 
 Solvent mask in the Olex 2 was used to deal with the disordered solvents. And the results are in line with the TGA and EA data.
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C22-C21
 2.5 with sigma of 0.02
 C22-O5
 1.2 with sigma of 0.02
 N2-C23
 1.5 with sigma of 0.02
 C23-O5
 2.5 with sigma of 0.02
 C19-C20
 2.5 with sigma of 0.02
 N1-C19 = N1-C20 = N2_$1-C22_$1 = N2_$1-C21_$1
 1.5 with sigma of 0.02
 C20-H1B
 1.9 with sigma of 0.02
 C19-H1B
 1.9 with sigma of 0.02
 H1B-H1A
 1.5 with sigma of 0.02
 O3-H3
 0.82 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O5 \\sim N2 \\sim C21 \\sim C22 \\sim C23: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
N2 \\sim C21 \\sim C22 \\sim N1 \\sim C19 \\sim C20: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(N2) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(O5)
\\sim Ueq, Uanis(C23) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(N1) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(N2) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 O5, N2, C21, C22, C23
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N2, C21, C22, N1, C19, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Fixed Sof: O5(0.5) N2(0.5) C21(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C22(0.5)
 H22(0.5) C23(0.5) H23A(0.5) H23B(0.5) H23C(0.5) N1(0.5) H1A(0.5) C19(0.5)
 H19A(0.5) H19B(0.5) H19C(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5)
6.a Riding coordinates:
 N1(H1A), C19(H19A,H19B,H19C)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3A), C4(H4), C6(H6), C7(H7), C13(H13), C14(H14), C16(H16), C17(H17),
 C22(H22)
6.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C20(H20A,H20B,H20C)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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
Cu1 Cu 0.7500 0.7500 1.0000 0.0539(2) Uani 1 2 d S T P . .
S1 S 0.56541(3) 0.50175(2) 0.85756(7) 0.0257(2) Uani 1 1 d . . . . .
S2 S 0.43919(3) 0.40834(2) 0.62888(7) 0.02247(19) Uani 1 1 d . . . . .
O1 O 0.70287(15) 0.70461(6) 0.9542(3) 0.0532(7) Uani 1 1 d . . . . .
O2 O 0.74465(12) 0.67075(6) 1.1593(3) 0.0403(5) Uani 1 1 d . . . . .
O3 O 0.29833(12) 0.22637(6) 0.3271(3) 0.0397(5) Uani 1 1 d D . . . .
H3 H 0.288(2) 0.2095(10) 0.267(4) 0.062(13) Uiso 1 1 d D . . . .
O4 O 0.40054(13) 0.21946(7) 0.2354(3) 0.0526(7) Uani 1 1 d . . . . .
C1 C 0.70722(16) 0.67467(8) 1.0348(3) 0.0321(6) Uani 1 1 d . . . . .
C2 C 0.66241(14) 0.64131(7) 0.9727(3) 0.0269(5) Uani 1 1 d . . . . .
C3 C 0.62300(16) 0.64371(7) 0.8287(3) 0.0301(6) Uani 1 1 d . . . . .
H3A H 0.6254 0.6659 0.7707 0.036 Uiso 1 1 calc R . . . .
C4 C 0.58064(15) 0.61349(7) 0.7719(3) 0.0274(6) Uani 1 1 d . . . . .
H4 H 0.5554 0.6153 0.6753 0.033 Uiso 1 1 calc R . . . .
C5 C 0.57530(13) 0.58005(7) 0.8585(3) 0.0207(5) Uani 1 1 d . . . . .
C6 C 0.61536(13) 0.57754(7) 1.0014(3) 0.0233(5) Uani 1 1 d . . . . .
H6 H 0.6130 0.5554 1.0595 0.028 Uiso 1 1 calc R . . . .
C7 C 0.65874(14) 0.60780(7) 1.0579(3) 0.0266(5) Uani 1 1 d . . . . .
H7 H 0.6854 0.6057 1.1529 0.032 Uiso 1 1 calc R . . . .
C8 C 0.53044(13) 0.54718(6) 0.7983(3) 0.0202(5) Uani 1 1 d . . . . .
C9 C 0.5000 0.47446(9) 0.7500 0.0209(7) Uani 1 2 d S T P . .
C10 C 0.5000 0.43563(9) 0.7500 0.0195(6) Uani 1 2 d S T P . .
C11 C 0.47288(14) 0.36314(6) 0.6932(3) 0.0224(5) Uani 1 1 d . . . . .
C12 C 0.44394(13) 0.32910(7) 0.6056(3) 0.0218(5) Uani 1 1 d . . . . .
C13 C 0.37186(15) 0.32114(8) 0.5845(3) 0.0284(6) Uani 1 1 d . . . . .
H13 H 0.3411 0.3368 0.6298 0.034 Uiso 1 1 calc R . . . .
C14 C 0.34604(15) 0.29000(8) 0.4963(3) 0.0296(6) Uani 1 1 d . . . . .
H14 H 0.2983 0.2841 0.4861 0.036 Uiso 1 1 calc R . . . .
C15 C 0.39141(15) 0.26742(7) 0.4229(3) 0.0265(5) Uani 1 1 d . . . . .
C16 C 0.46327(15) 0.27531(7) 0.4432(3) 0.0270(5) Uani 1 1 d . . . . .
H16 H 0.4938 0.2602 0.3951 0.032 Uiso 1 1 calc R . . . .
C17 C 0.48929(14) 0.30574(7) 0.5356(3) 0.0254(5) Uani 1 1 d . . . . .
H17 H 0.5374 0.3106 0.5510 0.030 Uiso 1 1 calc R . . . .
C18 C 0.36423(16) 0.23511(8) 0.3188(3) 0.0329(6) Uani 1 1 d . . . . .
O5 O 0.6396(8) 0.1278(3) 0.5861(14) 0.152(4) Uani 0.5 1 d D U . . .
N2 N 0.6205(6) 0.1864(3) 0.7173(11) 0.099(3) Uani 0.5 1 d D U . . .
C21 C 0.6137(6) 0.2262(2) 0.6878(10) 0.065(2) Uani 0.5 1 d D U . . .
H21A H 0.6323 0.2322 0.5953 0.097 Uiso 0.5 1 calc GR . . . .
H21B H 0.6392 0.2404 0.7702 0.097 Uiso 0.5 1 calc GR . . . .
H21C H 0.5648 0.2333 0.6777 0.097 Uiso 0.5 1 calc GR . . . .
C22 C 0.6251(8) 0.1613(3) 0.5819(14) 0.099(3) Uani 0.5 1 d D U . . .
H22 H 0.6158 0.1727 0.4866 0.119 Uiso 0.5 1 calc R . . . .
C23 C 0.6620(11) 0.1659(5) 0.8403(17) 0.166(6) Uani 0.5 1 d D U . . .
H23A H 0.7040 0.1802 0.8741 0.249 Uiso 0.5 1 calc GR . . . .
H23B H 0.6746 0.1410 0.8051 0.249 Uiso 0.5 1 calc GR . . . .
H23C H 0.6350 0.1628 0.9231 0.249 Uiso 0.5 1 calc GR . . . .
N1 N 0.7238(8) 0.5561(5) 0.624(2) 0.150(5) Uani 0.5 1 d D U . . .
H1A H 0.6832 0.5631 0.6453 0.180 Uiso 0.5 1 d DR . . . .
H1B H 0.7271(19) 0.5443(8) 0.537(2) 0.21(5) Uiso 1 1 d D . . . .
C19 C 0.7619(7) 0.5345(4) 0.7415(15) 0.101(4) Uani 0.5 1 d D U . . .
H19A H 0.8113 0.5356 0.7333 0.152 Uiso 0.5 1 d R . . . .
H19B H 0.7473 0.5080 0.7428 0.152 Uiso 0.5 1 d R . . . .
H19C H 0.7530 0.5469 0.8337 0.152 Uiso 0.5 1 d R . . . .
C20 C 0.7534(12) 0.5949(5) 0.590(3) 0.184(7) Uani 0.5 1 d D U . . .
H20A H 0.7206 0.6147 0.6090 0.276 Uiso 0.5 1 calc GR . . . .
H20B H 0.7613 0.5959 0.4858 0.276 Uiso 0.5 1 calc GR . . . .
H20C H 0.7971 0.5989 0.6545 0.276 Uiso 0.5 1 calc GR . . . .


_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
Cu1 O1 1.835(2) 7_667 ?
Cu1 O1 1.835(2) . ?
S1 C8 1.766(2) . ?
S1 C9 1.7508(18) . ?
S2 C10 1.7555(17) . ?
S2 C11 1.763(2) . ?
O1 C1 1.258(4) . ?
O2 C1 1.244(4) . ?
O3 H3 0.801(19) . ?
O3 C18 1.310(4) . ?
O4 C18 1.210(4) . ?
C1 C2 1.502(3) . ?
C2 C3 1.399(4) . ?
C2 C7 1.395(4) . ?
C3 H3A 0.9300 . ?
C3 C4 1.380(3) . ?
C4 H4 0.9300 . ?
C4 C5 1.403(3) . ?
C5 C6 1.397(3) . ?
C5 C8 1.485(3) . ?
C6 H6 0.9300 . ?
C6 C7 1.391(3) . ?
C7 H7 0.9300 . ?
C8 C8 1.354(5) 2_656 ?
C9 S1 1.7507(18) 2_656 ?
C9 C10 1.347(4) . ?
C10 S2 1.7555(17) 2_656 ?
C11 C11 1.350(5) 2_656 ?
C11 C12 1.482(3) . ?
C12 C13 1.397(4) . ?
C12 C17 1.393(4) . ?
C13 H13 0.9300 . ?
C13 C14 1.387(4) . ?
C14 H14 0.9300 . ?
C14 C15 1.395(4) . ?
C15 C16 1.392(4) . ?
C15 C18 1.502(3) . ?
C16 H16 0.9300 . ?
C16 C17 1.389(3) . ?
C17 H17 0.9300 . ?
O5 C22 1.194(12) . ?
N2 C21 1.409(10) . ?
N2 C22 1.498(12) . ?
N2 C23 1.451(14) . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 H22 0.9300 . ?
C23 H23A 0.9600 . ?
C23 H23B 0.9600 . ?
C23 H23C 0.9600 . ?
N1 H1A 0.8598 . ?
N1 H1B 0.89(2) . ?
N1 C19 1.412(14) . ?
N1 C20 1.505(15) . ?
C19 H19A 0.9598 . ?
C19 H19B 0.9604 . ?
C19 H19C 0.9601 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?

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 Cu1 O1 180.0 7_667 . ?
C9 S1 C8 95.97(12) . . ?
C10 S2 C11 95.53(12) . . ?
C1 O1 Cu1 126.1(2) . . ?
C18 O3 H3 107(3) . . ?
O1 C1 C2 115.8(3) . . ?
O2 C1 O1 125.7(2) . . ?
O2 C1 C2 118.5(2) . . ?
C3 C2 C1 120.2(2) . . ?
C7 C2 C1 120.7(2) . . ?
C7 C2 C3 119.1(2) . . ?
C2 C3 H3A 119.7 . . ?
C4 C3 C2 120.6(2) . . ?
C4 C3 H3A 119.7 . . ?
C3 C4 H4 119.7 . . ?
C3 C4 C5 120.7(2) . . ?
C5 C4 H4 119.7 . . ?
C4 C5 C8 121.2(2) . . ?
C6 C5 C4 118.6(2) . . ?
C6 C5 C8 120.1(2) . . ?
C5 C6 H6 119.6 . . ?
C7 C6 C5 120.8(2) . . ?
C7 C6 H6 119.6 . . ?
C2 C7 H7 119.9 . . ?
C6 C7 C2 120.3(2) . . ?
C6 C7 H7 119.9 . . ?
C5 C8 S1 113.55(17) . . ?
C8 C8 S1 116.76(8) 2_656 . ?
C8 C8 C5 129.62(13) 2_656 . ?
S1 C9 S1 114.50(18) 2_656 . ?
C10 C9 S1 122.75(9) . 2_656 ?
C10 C9 S1 122.75(9) . . ?
S2 C10 S2 114.70(17) 2_656 . ?
C9 C10 S2 122.65(9) . 2_656 ?
C9 C10 S2 122.65(9) . . ?
C11 C11 S2 117.08(8) 2_656 . ?
C11 C11 C12 126.21(14) 2_656 . ?
C12 C11 S2 116.34(17) . . ?
C13 C12 C11 121.5(2) . . ?
C17 C12 C11 119.1(2) . . ?
C17 C12 C13 119.3(2) . . ?
C12 C13 H13 119.9 . . ?
C14 C13 C12 120.2(3) . . ?
C14 C13 H13 119.9 . . ?
C13 C14 H14 119.9 . . ?
C13 C14 C15 120.3(3) . . ?
C15 C14 H14 119.9 . . ?
C14 C15 C18 121.3(2) . . ?
C16 C15 C14 119.7(2) . . ?
C16 C15 C18 118.9(2) . . ?
C15 C16 H16 120.1 . . ?
C17 C16 C15 119.9(2) . . ?
C17 C16 H16 120.1 . . ?
C12 C17 H17 119.7 . . ?
C16 C17 C12 120.6(2) . . ?
C16 C17 H17 119.7 . . ?
O3 C18 C15 113.4(2) . . ?
O4 C18 O3 124.5(2) . . ?
O4 C18 C15 122.1(3) . . ?
C21 N2 C22 115.8(9) . . ?
C21 N2 C23 130.6(11) . . ?
C23 N2 C22 103.6(11) . . ?
N2 C21 H21A 109.5 . . ?
N2 C21 H21B 109.5 . . ?
N2 C21 H21C 109.5 . . ?
H21A C21 H21B 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
O5 C22 N2 125.4(12) . . ?
O5 C22 H22 117.3 . . ?
N2 C22 H22 117.3 . . ?
N2 C23 H23A 109.5 . . ?
N2 C23 H23B 109.5 . . ?
N2 C23 H23C 109.5 . . ?
H23A C23 H23B 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
H1A N1 H1B 119.8 . . ?
C19 N1 H1A 112.3 . . ?
C19 N1 H1B 108.1(18) . . ?
C19 N1 C20 116.8(14) . . ?
C20 N1 H1A 99.6 . . ?
C20 N1 H1B 99.8(19) . . ?
N1 C19 H19A 110.0 . . ?
N1 C19 H19B 113.2 . . ?
N1 C19 H19C 105.1 . . ?
H19A C19 H19B 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
N1 C20 H20A 109.5 . . ?
N1 C20 H20B 109.5 . . ?
N1 C20 H20C 109.5 . . ?
H20A C20 H20B 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O3 H3 O2 0.801(19) 1.79(2) 2.569(3) 165(5) 3_444

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
Cu1 O1 C1 O2 -0.4(5) . . . . ?
Cu1 O1 C1 C2 179.3(2) . . . . ?
S1 C9 C10 S2 -173.85(4) . . . . ?
S1 C9 C10 S2 6.15(4) 2_656 . . . ?
S1 C9 C10 S2 -173.85(4) 2_656 . . 2_656 ?
S1 C9 C10 S2 6.15(4) . . . 2_656 ?
S2 C11 C12 C13 -57.3(3) . . . . ?
S2 C11 C12 C17 119.1(2) . . . . ?
O1 C1 C2 C3 4.4(4) . . . . ?
O1 C1 C2 C7 -174.8(3) . . . . ?
O2 C1 C2 C3 -175.9(3) . . . . ?
O2 C1 C2 C7 4.8(4) . . . . ?
C1 C2 C3 C4 -178.8(3) . . . . ?
C1 C2 C7 C6 178.0(3) . . . . ?
C2 C3 C4 C5 1.1(4) . . . . ?
C3 C2 C7 C6 -1.3(4) . . . . ?
C3 C4 C5 C6 -1.9(4) . . . . ?
C3 C4 C5 C8 -179.5(3) . . . . ?
C4 C5 C6 C7 1.1(4) . . . . ?
C4 C5 C8 S1 145.0(2) . . . . ?
C4 C5 C8 C8 -31.9(5) . . . 2_656 ?
C5 C6 C7 C2 0.5(4) . . . . ?
C6 C5 C8 S1 -32.5(3) . . . . ?
C6 C5 C8 C8 150.6(4) . . . 2_656 ?
C7 C2 C3 C4 0.5(4) . . . . ?
C8 S1 C9 S1 -0.42(8) . . . 2_656 ?
C8 S1 C9 C10 179.58(8) . . . . ?
C8 C5 C6 C7 178.7(2) . . . . ?
C9 S1 C8 C5 -175.84(17) . . . . ?
C9 S1 C8 C8 1.5(3) . . . 2_656 ?
C10 S2 C11 C11 2.2(3) . . . 2_656 ?
C10 S2 C11 C12 -171.23(19) . . . . ?
C11 S2 C10 S2 -0.64(9) . . . 2_656 ?
C11 S2 C10 C9 179.37(9) . . . . ?
C11 C11 C12 C13 129.9(4) 2_656 . . . ?
C11 C11 C12 C17 -53.7(5) 2_656 . . . ?
C11 C12 C13 C14 177.2(2) . . . . ?
C11 C12 C17 C16 -175.1(2) . . . . ?
C12 C13 C14 C15 -2.7(4) . . . . ?
C13 C12 C17 C16 1.4(4) . . . . ?
C13 C14 C15 C16 2.6(4) . . . . ?
C13 C14 C15 C18 -176.1(3) . . . . ?
C14 C15 C16 C17 -0.4(4) . . . . ?
C14 C15 C18 O3 -11.6(4) . . . . ?
C14 C15 C18 O4 167.6(3) . . . . ?
C15 C16 C17 C12 -1.5(4) . . . . ?
C16 C15 C18 O3 169.7(3) . . . . ?
C16 C15 C18 O4 -11.1(4) . . . . ?
C17 C12 C13 C14 0.8(4) . . . . ?
C18 C15 C16 C17 178.2(2) . . . . ?
C21 N2 C22 O5 170.2(16) . . . . ?
C23 N2 C22 O5 21(2) . . . . ?

_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 0.000 0.500 -0.314 763.1 32.7 0.5(C3H7NO)
2 0.500 0.000 -0.736 763.1 32.7 2(H2O)


_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_CuII_TTFTB
_database_code_depnum_ccdc_archive 'CCDC 2082446'
loop_
_audit_author_name
_audit_author_address
'Jian Su'
;Nanjing University
China
;
_audit_update_record             
;
2021-10-07 deposited with the CCDC.	2021-10-11 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT420_CuII_TTFTB          
;
PROBLEM: D-H Bond Without Acceptor  O5       --H5B      .     Please Check
RESPONSE: Response: This is caused by the remove of guest solvents.
;
# Added during the CSD deposition process: Thursday 07 October 2021 07:20 AM
# end Validation Reply Form

_audit_creation_date             2021-10-06
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '0.5(C68 H40 Cu2 O18 S8)'
_chemical_formula_sum            'C34 H20 Cu O9 S4'
_chemical_formula_weight         764.28
_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'
Cu Cu 0.3201 1.2651 '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'
S S 0.1246 0.1234 '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      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   18.757(4)
_cell_length_b                   35.559(7)
_cell_length_c                   8.899(2)
_cell_angle_alpha                90
_cell_angle_beta                 101.17(3)
_cell_angle_gamma                90
_cell_volume                     5823(2)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    2021
_cell_measurement_temperature    173
_cell_measurement_theta_max      24.95
_cell_measurement_theta_min      2.22
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.550
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5714
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0905 before and 0.0589 after correction.
The Ratio of minimum to maximum transmission is 0.7668.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    0.872
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       neddle-like
_exptl_crystal_F_000             1556
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1197
_diffrn_reflns_av_unetI/netI     0.1536
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            15760
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.387
_diffrn_reflns_theta_min         2.044
_diffrn_ambient_temperature      173
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.988
_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                   'fine-focus sealed tube'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2486
_reflns_number_total             5307
_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 v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    ?
_refine_diff_density_max         1.004
_refine_diff_density_min         -1.179
_refine_diff_density_rms         0.126
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         5307
_refine_ls_number_restraints     224
_refine_ls_R_factor_all          0.1728
_refine_ls_R_factor_gt           0.1094
_refine_ls_restrained_S_all      1.019
_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)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3075
_refine_ls_wR_factor_ref         0.3475
_refine_special_details          
; 
 Solvent mask in the Olex 2 was used to deal with the disordered solvents. And the results are in line with the TGA and EA data.
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 H3-O3
 0.84 with sigma of 0.02
 H3-O4
 2.29 with sigma of 0.02
 H3-C18
 1.76 with sigma of 0.02
 O3-C18
 1.2 with sigma of 0.02
 C2-C1 \\sim C18-C15
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(S2) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C10) \\sim
Ueq, Uanis(C9) \\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.005 and sigma
for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 S1, S2, C10, C11, C9, C12, C13, C17, C8, C14, C16, C5, C15, C6, C4, C18, C7,
 C3, O4, O3, O5, C2, C1, O1, O2, Cu1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: O5(0.5) H5A(0.5) H5B(0.5)
6.a Riding coordinates:
 O5(H5A,H5B)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C4(H4), C7(H7), C3(H3A), C13(H13), C14(H14), C17(H17), C16(H16)
;
_atom_sites_solution_hydrogens   mixed
_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
S2 S 0.56391(11) 0.41293(4) 0.8760(2) 0.0392(5) Uani 1 1 d . U . . .
S1 S 0.56881(10) 0.50393(4) 0.8633(2) 0.0388(5) Uani 1 1 d . U . . .
C8 C 0.5321(3) 0.54786(15) 0.8001(7) 0.0313(13) Uani 1 1 d . U . . .
C10 C 0.5000 0.4398(2) 0.7500 0.0248(15) Uani 1 2 d S TU P . .
C9 C 0.5000 0.4775(2) 0.7500 0.0269(15) Uani 1 2 d S TU P . .
O2 O 0.7476(4) 0.67214(16) 1.1721(7) 0.085(2) Uani 1 1 d . U . . .
C6 C 0.6196(4) 0.57892(18) 1.0106(8) 0.0419(16) Uani 1 1 d . U . . .
H6 H 0.6182 0.5575 1.0696 0.050 Uiso 1 1 calc R . . . .
C5 C 0.5775(4) 0.58041(17) 0.8646(8) 0.0401(15) Uani 1 1 d . U . . .
C4 C 0.5838(4) 0.61255(17) 0.7778(9) 0.0458(17) Uani 1 1 d . U . . .
H4 H 0.5595 0.6135 0.6764 0.055 Uiso 1 1 calc R . . . .
O3 O 0.6993(5) 0.2306(2) 1.1748(9) 0.103(2) Uani 1 1 d D U . . .
C7 C 0.6634(5) 0.6084(2) 1.0702(9) 0.0537(19) Uani 1 1 d . U . . .
H7 H 0.6909 0.6068 1.1689 0.064 Uiso 1 1 calc R . . . .
C3 C 0.6248(5) 0.6425(2) 0.8380(9) 0.059(2) Uani 1 1 d . U . . .
H3A H 0.6244 0.6643 0.7806 0.070 Uiso 1 1 calc R . . . .
C2 C 0.6668(4) 0.64068(18) 0.9834(9) 0.0498(17) Uani 1 1 d D U . . .
C13 C 0.5148(6) 0.3114(2) 0.9581(10) 0.069(2) Uani 1 1 d . U . . .
H13 H 0.4650 0.3160 0.9391 0.083 Uiso 1 1 calc R . . . .
C12 C 0.5593(5) 0.33540(18) 0.8948(8) 0.0524(14) Uani 1 1 d . U . . .
C11 C 0.5295(4) 0.36911(17) 0.8093(8) 0.0428(14) Uani 1 1 d . U . . .
C15 C 0.6090(6) 0.2731(2) 1.0657(10) 0.0719(18) Uani 1 1 d D U . . .
C14 C 0.5408(6) 0.2820(2) 1.0455(11) 0.085(3) Uani 1 1 d . U . . .
H14 H 0.5096 0.2678 1.0922 0.102 Uiso 1 1 calc R . . . .
C17 C 0.6318(6) 0.3273(2) 0.9194(10) 0.071(2) Uani 1 1 d . U . . .
H17 H 0.6638 0.3426 0.8795 0.086 Uiso 1 1 calc R . . . .
C16 C 0.6572(6) 0.2948(2) 1.0075(10) 0.077(2) Uani 1 1 d . U . . .
H16 H 0.7062 0.2885 1.0252 0.092 Uiso 1 1 calc R . . . .
C1 C 0.7089(6) 0.6754(2) 1.0500(11) 0.073(3) Uani 1 1 d D U . A 1
C18 C 0.6367(7) 0.2389(3) 1.1634(14) 0.102(3) Uani 1 1 d D U . . .
O4 O 0.6008(6) 0.2237(3) 1.2419(14) 0.186(5) Uani 1 1 d D U . . .
H3 H 0.719(2) 0.214(2) 1.231(11) 0.16(6) Uiso 1 1 d D . . . .
Cu1 Cu 0.7500 0.7500 1.0000 0.1721(15) Uani 1 2 d S TU P A 1
O1 O 0.7031(6) 0.7035(2) 0.9677(9) 0.144(3) Uani 1 1 d . U . A 1
O5 O 0.8535(13) 0.7221(5) 0.938(2) 0.176(6) Uani 0.5 1 d . U . A 1
H5A H 0.8914 0.7070 1.0034 0.263 Uiso 0.5 1 d R . . A 1
H5B H 0.8675 0.7212 0.8362 0.263 Uiso 0.5 1 d R . . A 1


_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
S2 C10 1.757(4) . ?
S2 C11 1.746(6) . ?
S1 C8 1.755(6) . ?
S1 C9 1.750(5) . ?
C8 C8 1.351(13) 2_656 ?
C8 C5 1.485(8) . ?
C10 S2 1.757(4) 2_656 ?
C10 C9 1.340(11) . ?
C9 S1 1.750(5) 2_656 ?
O2 C1 1.190(10) . ?
C6 C5 1.385(9) . ?
C6 C7 1.374(9) . ?
C5 C4 1.397(9) . ?
C4 C3 1.359(9) . ?
O3 C18 1.197(11) . ?
C7 C2 1.391(10) . ?
C3 C2 1.380(10) . ?
C2 C1 1.524(8) . ?
C13 C12 1.387(11) . ?
C13 C14 1.340(11) . ?
C12 C11 1.470(9) . ?
C12 C17 1.365(12) . ?
C11 C11 1.374(14) 2_656 ?
C15 C14 1.296(13) . ?
C15 C16 1.367(13) . ?
C15 C18 1.525(8) . ?
C17 C16 1.424(11) . ?
C1 O1 1.231(11) . ?
C18 O4 1.190(13) . ?
Cu1 O1 1.868(7) 7_667 ?
Cu1 O1 1.868(6) . ?
Cu1 O5 2.34(3) . ?
Cu1 O5 2.34(3) 7_667 ?

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
C11 S2 C10 96.2(3) . . ?
C9 S1 C8 95.4(3) . . ?
C8 C8 S1 117.1(2) 2_656 . ?
C8 C8 C5 128.7(4) 2_656 . ?
C5 C8 S1 114.2(5) . . ?
S2 C10 S2 114.1(4) 2_656 . ?
C9 C10 S2 123.0(2) . . ?
C9 C10 S2 123.0(2) . 2_656 ?
S1 C9 S1 115.0(4) 2_656 . ?
C10 C9 S1 122.5(2) . 2_656 ?
C10 C9 S1 122.5(2) . . ?
C7 C6 C5 121.6(7) . . ?
C6 C5 C8 120.9(6) . . ?
C6 C5 C4 117.1(6) . . ?
C4 C5 C8 121.9(7) . . ?
C3 C4 C5 121.6(7) . . ?
C6 C7 C2 120.2(7) . . ?
C4 C3 C2 120.7(7) . . ?
C7 C2 C1 121.9(7) . . ?
C3 C2 C7 118.7(7) . . ?
C3 C2 C1 119.1(7) . . ?
C14 C13 C12 122.4(10) . . ?
C13 C12 C11 120.8(8) . . ?
C17 C12 C13 117.7(8) . . ?
C17 C12 C11 121.5(8) . . ?
C12 C11 S2 118.3(5) . . ?
C11 C11 S2 116.8(2) 2_656 . ?
C11 C11 C12 124.5(4) 2_656 . ?
C14 C15 C16 121.1(8) . . ?
C14 C15 C18 119.4(10) . . ?
C16 C15 C18 119.4(10) . . ?
C15 C14 C13 120.7(10) . . ?
C12 C17 C16 118.5(9) . . ?
C15 C16 C17 119.5(10) . . ?
O2 C1 C2 117.0(8) . . ?
O2 C1 O1 126.2(8) . . ?
O1 C1 C2 116.6(8) . . ?
O3 C18 C15 117.8(11) . . ?
O4 C18 O3 119.7(9) . . ?
O4 C18 C15 121.9(11) . . ?
O1 Cu1 O1 180.0 7_667 . ?
O1 Cu1 O5 91.4(5) 7_667 . ?
O1 Cu1 O5 91.4(5) . 7_667 ?
O1 Cu1 O5 88.6(5) . . ?
O1 Cu1 O5 88.6(5) 7_667 7_667 ?
O5 Cu1 O5 180.0(6) . 7_667 ?
C1 O1 Cu1 129.9(7) . . ?

_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 0.000 0.500 -0.955 1447.9 46.2 '1(C6H12) and 0.5(NH2(CH3)2)'
2 0.500 0.000 -0.656 1447.9 46.2 1(C6H12)


_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_TTFTB_HOF
_database_code_depnum_ccdc_archive 'CCDC 2082447'
loop_
_audit_author_name
_audit_author_address
'Jian Su'
;Nanjing University
China
;
_audit_update_record             
;
2021-09-15 deposited with the CCDC.	2021-10-11 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT420_TTFTB_HOF           
;
PROBLEM: D-H Bond Without Acceptor  O4       --H4A      .     Please Check
RESPONSE: Response: This is caused by the remove of guest solvents.
;
# Added during the CSD deposition process: Wednesday 15 September 2021 05:33 AM
# end Validation Reply Form

_audit_creation_date             2021-09-09
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C34 H20 O8 S4'
_chemical_formula_sum            'C34 H20 O8 S4'
_chemical_formula_weight         684.74
_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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 '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      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   20.495(10)
_cell_length_b                   34.798(16)
_cell_length_c                   8.801(5)
_cell_angle_alpha                90
_cell_angle_beta                 102.997(13)
_cell_angle_gamma                90
_cell_volume                     6116(5)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    2604
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      23.88
_cell_measurement_theta_min      2.34
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.183
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5606
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1327 before and 0.0553 after correction.
The Ratio of minimum to maximum transmission is 0.7521.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    0.744
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle-like
_exptl_crystal_F_000             1408
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.10
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1139
_diffrn_reflns_av_unetI/netI     0.1337
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            21673
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.525
_diffrn_reflns_theta_min         2.030
_diffrn_ambient_temperature      296.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_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                   'fine-focus sealed tube'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2902
_reflns_number_total             6285
_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 v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    ?
_refine_diff_density_max         0.431
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.059
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.988
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     213
_refine_ls_number_reflns         6285
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.1327
_refine_ls_R_factor_gt           0.0713
_refine_ls_restrained_S_all      0.989
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1094P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2039
_refine_ls_wR_factor_ref         0.2313
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 O4-H4A
 0.86 with sigma of 0.02
 H4A-C18
 1.81 with sigma of 0.02
 H4A-O3
 2.4 with sigma of 0.02
3. Rigid bond restraints
 O4, C18
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
4.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C4(H4), C17(H17), C13(H13), C3(H3), C14(H14), C16(H16)
4.b Idealised tetrahedral OH refined as rotating group:
 O2(H2)
;
_atom_sites_solution_hydrogens   mixed
_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
S2 S 0.56034(6) 0.41246(3) 0.37929(13) 0.0422(3) Uani 1 1 d . . . . .
S1 S 0.56348(6) 0.50502(3) 0.36838(15) 0.0474(4) Uani 1 1 d . . . . .
O2 O 0.7364(2) 0.67217(10) 0.6987(5) 0.0811(12) Uani 1 1 d . . . . .
H2 H 0.7484 0.6931 0.7376 0.122 Uiso 1 1 calc GR . . . .
C10 C 0.5000 0.43971(14) 0.2500 0.0333(14) Uani 1 2 d S T P . .
C9 C 0.5000 0.47754(15) 0.2500 0.0375(14) Uani 1 2 d S T P . .
C11 C 0.52638(19) 0.36756(9) 0.3089(5) 0.0370(10) Uani 1 1 d . . . . .
C8 C 0.5301(2) 0.55037(10) 0.3053(5) 0.0394(11) Uani 1 1 d . . . . .
O3 O 0.7097(2) 0.23130(11) 0.6737(5) 0.1012(16) Uani 1 1 d D . . . .
C5 C 0.5726(2) 0.58295(10) 0.3714(5) 0.0407(11) Uani 1 1 d . . . . .
C12 C 0.5597(2) 0.33334(11) 0.3969(5) 0.0476(12) Uani 1 1 d . . . . .
C6 C 0.6129(2) 0.58020(11) 0.5177(5) 0.0447(11) Uani 1 1 d . . . . .
H6 H 0.6121 0.5579 0.5756 0.054 Uiso 1 1 calc R . . . .
C7 C 0.6558(2) 0.61092(12) 0.5824(5) 0.0524(13) Uani 1 1 d . . . . .
H7 H 0.6828 0.6091 0.6823 0.063 Uiso 1 1 calc R . . . .
C4 C 0.5780(2) 0.61543(11) 0.2849(5) 0.0511(12) Uani 1 1 d . . . . .
H4 H 0.5533 0.6171 0.1826 0.061 Uiso 1 1 calc R . . . .
C15 C 0.6180(3) 0.27028(12) 0.5700(6) 0.0578(14) Uani 1 1 d . . . . .
C2 C 0.6565(3) 0.64297(12) 0.4956(6) 0.0591(14) Uani 1 1 d . . . . .
C17 C 0.6281(2) 0.32610(12) 0.4162(6) 0.0553(13) Uani 1 1 d . . . . .
H17 H 0.6547 0.3419 0.3701 0.066 Uiso 1 1 calc R . . . .
C13 C 0.5204(2) 0.30847(12) 0.4636(6) 0.0586(14) Uani 1 1 d . . . . .
H13 H 0.4747 0.3127 0.4507 0.070 Uiso 1 1 calc R . . . .
O4 O 0.6163(2) 0.21847(13) 0.7383(7) 0.128(2) Uani 1 1 d D U . . .
C3 C 0.6180(3) 0.64463(12) 0.3457(6) 0.0602(14) Uani 1 1 d . . . . .
H3 H 0.6197 0.6664 0.2857 0.072 Uiso 1 1 calc R . . . .
C14 C 0.5511(3) 0.27744(12) 0.5491(6) 0.0644(15) Uani 1 1 d . . . . .
H14 H 0.5251 0.2609 0.5940 0.077 Uiso 1 1 calc R . . . .
O1 O 0.6987(3) 0.70706(13) 0.4886(6) 0.145(2) Uani 1 1 d . . . . .
C16 C 0.6550(3) 0.29545(13) 0.5035(6) 0.0607(14) Uani 1 1 d . . . . .
H16 H 0.7008 0.2913 0.5191 0.073 Uiso 1 1 calc R . . . .
C18 C 0.6495(4) 0.23644(15) 0.6633(8) 0.085(2) Uani 1 1 d D U . . .
C1 C 0.7005(3) 0.67701(16) 0.5627(8) 0.0812(19) Uani 1 1 d . . . . .
H4A H 0.6308(14) 0.2013(12) 0.800(5) 0.097 Uiso 1 1 d DR . . . .


_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
S2 C10 1.758(3) . ?
S2 C11 1.765(4) . ?
S1 C9 1.756(3) . ?
S1 C8 1.759(4) . ?
O2 C1 1.267(6) . ?
C10 S2 1.758(3) 2_655 ?
C10 C9 1.316(7) . ?
C9 S1 1.756(3) 2_655 ?
C11 C11 1.319(7) 2_655 ?
C11 C12 1.499(5) . ?
C8 C8 1.389(8) 2_655 ?
C8 C5 1.468(5) . ?
O3 C18 1.229(7) . ?
C5 C6 1.367(6) . ?
C5 C4 1.380(5) . ?
C12 C17 1.397(6) . ?
C12 C13 1.398(6) . ?
C6 C7 1.420(5) . ?
C7 C2 1.354(6) . ?
C4 C3 1.339(6) . ?
C15 C14 1.366(6) . ?
C15 C16 1.372(7) . ?
C15 C18 1.496(6) . ?
C2 C3 1.378(6) . ?
C2 C1 1.524(6) . ?
C17 C16 1.357(6) . ?
C13 C14 1.384(6) . ?
O4 C18 1.222(7) . ?
O1 C1 1.229(7) . ?

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
C10 S2 C11 94.92(18) . . ?
C9 S1 C8 96.76(19) . . ?
S2 C10 S2 114.7(3) . 2_655 ?
C9 C10 S2 122.65(13) . . ?
C9 C10 S2 122.65(14) . 2_655 ?
S1 C9 S1 114.0(3) 2_655 . ?
C10 C9 S1 123.01(14) . 2_655 ?
C10 C9 S1 123.01(14) . . ?
C11 C11 S2 117.70(12) 2_655 . ?
C11 C11 C12 127.2(2) 2_655 . ?
C12 C11 S2 115.1(3) . . ?
C8 C8 S1 116.24(13) 2_655 . ?
C8 C8 C5 129.2(2) 2_655 . ?
C5 C8 S1 114.4(3) . . ?
C6 C5 C8 119.8(4) . . ?
C6 C5 C4 118.1(4) . . ?
C4 C5 C8 121.8(4) . . ?
C17 C12 C11 122.3(4) . . ?
C17 C12 C13 119.7(4) . . ?
C13 C12 C11 118.0(4) . . ?
C5 C6 C7 120.9(4) . . ?
C2 C7 C6 118.6(4) . . ?
C3 C4 C5 121.2(4) . . ?
C14 C15 C16 117.4(4) . . ?
C14 C15 C18 120.9(5) . . ?
C16 C15 C18 121.7(5) . . ?
C7 C2 C3 119.9(4) . . ?
C7 C2 C1 120.1(5) . . ?
C3 C2 C1 120.0(5) . . ?
C16 C17 C12 118.6(5) . . ?
C14 C13 C12 118.5(5) . . ?
C4 C3 C2 121.2(4) . . ?
C15 C14 C13 122.4(5) . . ?
C17 C16 C15 123.4(5) . . ?
O3 C18 C15 117.2(6) . . ?
O4 C18 O3 123.9(5) . . ?
O4 C18 C15 118.4(6) . . ?
O2 C1 C2 115.4(5) . . ?
O1 C1 O2 123.8(5) . . ?
O1 C1 C2 120.7(6) . . ?

_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 0.000 0.500 -0.575 1745.5 431.2 0.5(Cu(OH)2(H2O)4)
2 0.500 0.000 -0.369 1745.5 431.2 1(CH3COCH3)


_olex2_submission_special_instructions 'No special instructions were received'
