# Electronic Supplementary Material (ESI) for Chemical Communications.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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_CuTua_a
_audit_block_doi                 10.5517/ccdc.csd.cc2bg7pr
_database_code_depnum_ccdc_archive 'CCDC 2158644'
loop_
_audit_author_name
_audit_author_address
'Kang Xiao'
;Nanjing University of Posts and Telecommications
China
;
_audit_update_record             
;
2023-05-18 deposited with the CCDC.	2023-07-17 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2019/2
_shelx_SHELXL_version_number     2019/2
_chemical_name_systematic        
'bis(μ-thiourea)-tetrakis(thiourea)-di-copper-(Cu-Cu) sulfate hydrate'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2Cu, 6[CH4N2S], SO4, H2O'
_chemical_formula_sum            'C6 H26 Cu2 N12 O5 S7'
_chemical_formula_weight         697.89

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'
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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

_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, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z-1/2'
'-x-1/2, y-1/2, z'

_cell_length_a                   19.2009(11)
_cell_length_b                   12.3001(7)
_cell_length_c                   21.4316(13)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     5061.6(5)
_cell_formula_units_Z            8
_cell_measurement_temperature    297(2)
_cell_measurement_reflns_used    9871
_cell_measurement_theta_min      2.69
_cell_measurement_theta_max      30.82

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.832
_exptl_crystal_F_000             2848
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    2.302
_shelx_estimated_absorpt_T_min   0.545
_shelx_estimated_absorpt_T_max   0.724
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5672
_exptl_absorpt_correction_T_max  0.7463
_exptl_absorpt_process_details   
'SADABS-2016; Bruker; Krause, L.,et al., J. Appl. Cryst. 48 (2015) 3-10'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      297(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'Bruker AXS area detector; Photon 100'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            53895
_diffrn_reflns_av_unetI/netI     0.0433
_diffrn_reflns_av_R_equivalents  0.0605
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_theta_min         2.691
_diffrn_reflns_theta_max         31.687
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             8539
_reflns_number_gt                5826
_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       'APEX III; Bruker AXS'
_computing_cell_refinement       'APEX III'
_computing_data_reduction        'SAINT; Bruker AXS'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_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)+(0.0276P)²+3.1237P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_extinction_coef       0.00064(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         8539
_refine_ls_number_parameters     298
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0752
_refine_ls_R_factor_gt           0.0376
_refine_ls_wR_factor_ref         0.0753
_refine_ls_wR_factor_gt          0.0656
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_restrained_S_all      1.004
_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
Cu1 Cu 0.62430(2) 0.26540(2) 0.32197(2) 0.02985(7) Uani 1 1 d . . . . .
O1 O 0.71603(9) -0.02399(13) 0.55095(8) 0.0359(4) Uani 1 1 d . . . . .
C1 C 0.71626(10) 0.37180(17) 0.20383(10) 0.0228(4) Uani 1 1 d . . . . .
S1 S 0.64124(3) 0.35339(4) 0.42013(2) 0.02498(11) Uani 1 1 d . . . . .
H1O H 0.5732(18) 0.0177(18) 0.5921(16) 0.081(12) Uiso 1 1 d D . . . .
N1 N 0.73461(10) 0.35646(15) 0.14553(8) 0.0323(4) Uani 1 1 d . . . . .
H1A H 0.732690 0.409420 0.119394 0.039 Uiso 1 1 calc R U . . .
H1B H 0.748552 0.293436 0.133455 0.039 Uiso 1 1 calc R U . . .
Cu2 Cu 0.55865(2) 0.45544(2) 0.36678(2) 0.02985(8) Uani 1 1 d . . . . .
O2 O 0.70965(9) -0.21612(13) 0.53218(7) 0.0373(4) Uani 1 1 d . . . . .
C2 C 0.64405(11) 0.67378(17) 0.40010(10) 0.0261(4) Uani 1 1 d . . . . .
S2 S 0.53585(3) 0.36021(4) 0.26672(2) 0.02256(11) Uani 1 1 d . . . . .
H2O H 0.554(2) 0.097(4) 0.6487(9) 0.112(16) Uiso 1 1 d D . . . .
N2 N 0.69502(11) 0.46891(16) 0.22152(9) 0.0372(5) Uani 1 1 d . . . . .
H2A H 0.693321 0.521255 0.194963 0.045 Uiso 1 1 calc R U . . .
H2B H 0.682859 0.479932 0.259619 0.045 Uiso 1 1 calc R U . . .
S3 S 0.72046(3) 0.26393(5) 0.25484(3) 0.02887(12) Uani 1 1 d . . . . .
N3 N 0.69176(10) 0.75088(16) 0.39717(10) 0.0372(5) Uani 1 1 d . . . . .
H3A H 0.704984 0.783459 0.430644 0.045 Uiso 1 1 calc R U . . .
H3B H 0.709623 0.768532 0.361796 0.045 Uiso 1 1 calc R U . . .
O3 O 0.60514(8) -0.11512(15) 0.55414(8) 0.0418(4) Uani 1 1 d . . . . .
C3 C 0.41026(12) 0.56970(18) 0.36570(11) 0.0286(5) Uani 1 1 d . . . . .
N4 N 0.61833(13) 0.64961(19) 0.45489(10) 0.0512(6) Uani 1 1 d . . . . .
H4A H 0.632575 0.683599 0.487548 0.061 Uiso 1 1 calc R U . . .
H4B H 0.587168 0.599725 0.458246 0.061 Uiso 1 1 calc R U . . .
O4 O 0.68915(8) -0.14731(12) 0.63494(7) 0.0280(3) Uani 1 1 d . . . . .
C4 C 0.45491(11) 0.30484(17) 0.28298(10) 0.0247(4) Uani 1 1 d . . . . .
S4 S 0.60167(4) 0.07960(5) 0.32902(3) 0.03743(15) Uani 1 1 d . . . . .
N5 N 0.44203(12) 0.63000(19) 0.32414(11) 0.0473(6) Uani 1 1 d . . . . .
H5A H 0.418274 0.671908 0.300088 0.057 Uiso 1 1 calc R U . . .
H5B H 0.486650 0.627675 0.320908 0.057 Uiso 1 1 calc R U . . .
O5 O 0.55668(10) 0.08724(18) 0.60412(10) 0.0486(5) Uani 1 1 d D . . . .
C5 C 0.62819(13) 0.03139(17) 0.40060(11) 0.0308(5) Uani 1 1 d . . . . .
S5 S 0.61860(3) 0.60889(5) 0.33334(3) 0.02877(12) Uani 1 1 d . . . . .
N6 N 0.34186(11) 0.57661(19) 0.36853(12) 0.0486(6) Uani 1 1 d . . . . .
H6A H 0.319888 0.619473 0.343687 0.058 Uiso 1 1 calc R U . . .
H6B H 0.319188 0.538243 0.395232 0.058 Uiso 1 1 calc R U . . .
C6 C 0.60106(12) 0.27314(17) 0.47559(10) 0.0270(4) Uani 1 1 d . . . . .
S6 S 0.45452(3) 0.48640(5) 0.41573(3) 0.03394(14) Uani 1 1 d . . . . .
N7 N 0.39901(10) 0.35230(17) 0.26097(10) 0.0383(5) Uani 1 1 d . . . . .
H7A H 0.358535 0.325671 0.268838 0.046 Uiso 1 1 calc R U . . .
H7B H 0.402772 0.410098 0.238637 0.046 Uiso 1 1 calc R U . . .
S7 S 0.67985(3) -0.12571(4) 0.56781(2) 0.02225(11) Uani 1 1 d . . . . .
N8 N 0.44855(11) 0.21675(17) 0.31698(10) 0.0374(5) Uani 1 1 d . . . . .
H8A H 0.407912 0.190583 0.324658 0.045 Uiso 1 1 calc R U . . .
H8B H 0.485025 0.185145 0.331591 0.045 Uiso 1 1 calc R U . . .
N9 N 0.58466(12) -0.0257(2) 0.43405(11) 0.0501(6) Uani 1 1 d . . . . .
H9A H 0.597548 -0.051626 0.469480 0.060 Uiso 1 1 calc R U . . .
H9B H 0.543109 -0.037332 0.420648 0.060 Uiso 1 1 calc R U . . .
N10 N 0.69097(12) 0.04814(19) 0.42176(11) 0.0499(6) Uani 1 1 d . . . . .
H10A H 0.703187 0.021728 0.457267 0.060 Uiso 1 1 calc R U . . .
H10B H 0.720156 0.085586 0.400202 0.060 Uiso 1 1 calc R U . . .
N11 N 0.63784(12) 0.23859(17) 0.52296(9) 0.0427(5) Uani 1 1 d . . . . .
H11A H 0.618688 0.198976 0.551220 0.051 Uiso 1 1 calc R U . . .
H11B H 0.681186 0.255484 0.525847 0.051 Uiso 1 1 calc R U . . .
N12 N 0.53481(11) 0.24683(17) 0.47162(11) 0.0434(5) Uani 1 1 d . . . . .
H12A H 0.515995 0.207184 0.500057 0.052 Uiso 1 1 calc R U . . .
H12B H 0.510306 0.269265 0.440599 0.052 Uiso 1 1 calc R U . . .


_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 S4 2.3312(7) . ?
Cu1 S3 2.3407(6) . ?
Cu1 S2 2.3763(6) . ?
Cu1 S1 2.3881(6) . ?
Cu1 Cu2 2.8241(4) . ?
O1 S7 1.4760(16) . ?
C1 N1 1.312(3) . ?
C1 N2 1.318(3) . ?
C1 S3 1.721(2) . ?
S1 C6 1.727(2) . ?
S1 Cu2 2.3233(6) . ?
N1 H1A 0.8600 . ?
N1 H1B 0.8600 . ?
Cu2 S6 2.2897(6) . ?
Cu2 S5 2.3240(6) . ?
Cu2 S2 2.4825(6) . ?
O2 S7 1.4654(17) . ?
C2 N4 1.308(3) . ?
C2 N3 1.320(3) . ?
C2 S5 1.710(2) . ?
S2 C4 1.732(2) . ?
N2 H2A 0.8600 . ?
N2 H2B 0.8600 . ?
N3 H3A 0.8600 . ?
N3 H3B 0.8600 . ?
O3 S7 1.4698(17) . ?
C3 N5 1.310(3) . ?
C3 N6 1.317(3) . ?
C3 S6 1.709(2) . ?
N4 H4A 0.8600 . ?
N4 H4B 0.8600 . ?
O4 S7 1.4739(15) . ?
C4 N7 1.310(3) . ?
C4 N8 1.311(3) . ?
S4 C5 1.722(2) . ?
N5 H5A 0.8600 . ?
N5 H5B 0.8600 . ?
O5 H1O 0.948(18) . ?
O5 H2O 0.964(18) . ?
C5 N10 1.304(3) . ?
C5 N9 1.306(3) . ?
N6 H6A 0.8600 . ?
N6 H6B 0.8600 . ?
C6 N11 1.308(3) . ?
C6 N12 1.315(3) . ?
N7 H7A 0.8600 . ?
N7 H7B 0.8600 . ?
N8 H8A 0.8600 . ?
N8 H8B 0.8600 . ?
N9 H9A 0.8600 . ?
N9 H9B 0.8600 . ?
N10 H10A 0.8600 . ?
N10 H10B 0.8600 . ?
N11 H11A 0.8600 . ?
N11 H11B 0.8600 . ?
N12 H12A 0.8600 . ?
N12 H12B 0.8600 . ?

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
S4 Cu1 S3 100.33(2) . . ?
S4 Cu1 S2 112.35(2) . . ?
S3 Cu1 S2 105.15(2) . . ?
S4 Cu1 S1 114.36(2) . . ?
S3 Cu1 S1 115.94(2) . . ?
S2 Cu1 S1 108.29(2) . . ?
S4 Cu1 Cu2 134.92(2) . . ?
S3 Cu1 Cu2 124.576(18) . . ?
S2 Cu1 Cu2 56.236(15) . . ?
S1 Cu1 Cu2 52.126(15) . . ?
N1 C1 N2 119.17(19) . . ?
N1 C1 S3 118.78(16) . . ?
N2 C1 S3 122.05(16) . . ?
C6 S1 Cu2 110.03(8) . . ?
C6 S1 Cu1 106.64(8) . . ?
Cu2 S1 Cu1 73.643(18) . . ?
C1 N1 H1A 120.0 . . ?
C1 N1 H1B 120.0 . . ?
H1A N1 H1B 120.0 . . ?
S6 Cu2 S1 117.41(2) . . ?
S6 Cu2 S5 116.02(2) . . ?
S1 Cu2 S5 104.62(2) . . ?
S6 Cu2 S2 108.68(2) . . ?
S1 Cu2 S2 106.89(2) . . ?
S5 Cu2 S2 101.78(2) . . ?
S6 Cu2 Cu1 133.10(2) . . ?
S1 Cu2 Cu1 54.232(16) . . ?
S5 Cu2 Cu1 110.260(19) . . ?
S2 Cu2 Cu1 52.728(14) . . ?
N4 C2 N3 117.9(2) . . ?
N4 C2 S5 122.49(17) . . ?
N3 C2 S5 119.61(17) . . ?
C4 S2 Cu1 110.36(8) . . ?
C4 S2 Cu2 99.78(7) . . ?
Cu1 S2 Cu2 71.036(17) . . ?
C1 N2 H2A 120.0 . . ?
C1 N2 H2B 120.0 . . ?
H2A N2 H2B 120.0 . . ?
C1 S3 Cu1 110.33(7) . . ?
C2 N3 H3A 120.0 . . ?
C2 N3 H3B 120.0 . . ?
H3A N3 H3B 120.0 . . ?
N5 C3 N6 117.3(2) . . ?
N5 C3 S6 122.30(18) . . ?
N6 C3 S6 120.4(2) . . ?
C2 N4 H4A 120.0 . . ?
C2 N4 H4B 120.0 . . ?
H4A N4 H4B 120.0 . . ?
N7 C4 N8 119.5(2) . . ?
N7 C4 S2 119.17(17) . . ?
N8 C4 S2 121.35(17) . . ?
C5 S4 Cu1 109.89(8) . . ?
C3 N5 H5A 120.0 . . ?
C3 N5 H5B 120.0 . . ?
H5A N5 H5B 120.0 . . ?
H1O O5 H2O 113(3) . . ?
N10 C5 N9 119.1(2) . . ?
N10 C5 S4 121.92(19) . . ?
N9 C5 S4 119.01(19) . . ?
C2 S5 Cu2 105.23(8) . . ?
C3 N6 H6A 120.0 . . ?
C3 N6 H6B 120.0 . . ?
H6A N6 H6B 120.0 . . ?
N11 C6 N12 119.5(2) . . ?
N11 C6 S1 118.61(18) . . ?
N12 C6 S1 121.89(18) . . ?
C3 S6 Cu2 104.27(8) . . ?
C4 N7 H7A 120.0 . . ?
C4 N7 H7B 120.0 . . ?
H7A N7 H7B 120.0 . . ?
O2 S7 O3 110.15(11) . . ?
O2 S7 O4 108.93(10) . . ?
O3 S7 O4 109.20(9) . . ?
O2 S7 O1 109.38(10) . . ?
O3 S7 O1 109.60(10) . . ?
O4 S7 O1 109.56(9) . . ?
C4 N8 H8A 120.0 . . ?
C4 N8 H8B 120.0 . . ?
H8A N8 H8B 120.0 . . ?
C5 N9 H9A 120.0 . . ?
C5 N9 H9B 120.0 . . ?
H9A N9 H9B 120.0 . . ?
C5 N10 H10A 120.0 . . ?
C5 N10 H10B 120.0 . . ?
H10A N10 H10B 120.0 . . ?
C6 N11 H11A 120.0 . . ?
C6 N11 H11B 120.0 . . ?
H11A N11 H11B 120.0 . . ?
C6 N12 H12A 120.0 . . ?
C6 N12 H12B 120.0 . . ?
H12A N12 H12B 120.0 . . ?

_refine_diff_density_max         0.497
_refine_diff_density_min         -0.422
_refine_diff_density_rms         0.086



