# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_ZJNU-15
_database_code_depnum_ccdc_archive 'CCDC 1981353'
loop_
_audit_author_name
_audit_author_address
'Yabing He' 'Zhejiang Normal University'
_audit_update_record             
;
2020-02-02 deposited with the CCDC.	2020-02-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '[Cu4OL3(H2O)].3.5DMF'
_chemical_formula_sum            'C49.50 H50.50 Cu4 N9.50 O17.50'
_chemical_formula_weight         1312.65

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'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           167
_space_group_name_H-M_alt        'R -3 c :H'
_space_group_name_Hall           '-R 3 2"c'

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

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'y, x, -z+1/2'
'x-y, -y, -z+1/2'
'-x, -x+y, -z+1/2'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'y+2/3, x+1/3, -z+5/6'
'x-y+2/3, -y+1/3, -z+5/6'
'-x+2/3, -x+y+1/3, -z+5/6'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'y+1/3, x+2/3, -z+7/6'
'x-y+1/3, -y+2/3, -z+7/6'
'-x+1/3, -x+y+2/3, -z+7/6'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-y, -x, z-1/2'
'-x+y, y, z-1/2'
'x, x-y, z-1/2'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-y+2/3, -x+1/3, z-1/6'
'-x+y+2/3, y+1/3, z-1/6'
'x+2/3, x-y+1/3, z-1/6'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'
'-y+1/3, -x+2/3, z+1/6'
'-x+y+1/3, y+2/3, z+1/6'
'x+1/3, x-y+2/3, z+1/6'

_cell_length_a                   18.4889(6)
_cell_length_b                   18.4889(6)
_cell_length_c                   55.2602(18)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     16359.3(12)
_cell_formula_units_Z            12
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    46837
_cell_measurement_theta_min      2.5
_cell_measurement_theta_max      27.5

_exptl_crystal_description       block
_exptl_crystal_colour            bule
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.599
_exptl_crystal_F_000             8040
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.120
_exptl_crystal_size_mid          0.110
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    1.619
_shelx_estimated_absorpt_T_min   0.829
_shelx_estimated_absorpt_T_max   0.855
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.823
_exptl_absorpt_correction_T_max  0.851
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON II'
_diffrn_measurement_method       'omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            46837
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_av_R_equivalents  0.0379
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -71
_diffrn_reflns_limit_l_max       70
_diffrn_reflns_theta_min         2.465
_diffrn_reflns_theta_max         27.486
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4170
_reflns_number_gt                3811
_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4170
_refine_ls_number_parameters     190
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0495
_refine_ls_R_factor_gt           0.0458
_refine_ls_wR_factor_ref         0.2129
_refine_ls_wR_factor_gt          0.2036
_refine_ls_goodness_of_fit_ref   1.004
_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 0.6667 0.3333 0.46087(2) 0.0302(3) Uani 1 3 d S T P . .
Cu2 Cu 0.69662(2) 0.44309(2) 0.50981(2) 0.0132(2) Uani 1 1 d . . . . .
O1 O 0.5852(2) 0.37354(19) 0.45716(5) 0.0418(8) Uani 1 1 d . . . . .
O1W O 0.6667 0.3333 0.42573(9) 0.0498(13) Uani 1 3 d S T P . .
O2 O 0.63516(14) 0.47087(13) 0.48643(4) 0.0206(5) Uani 1 1 d . . . . .
O3 O 0.53676(15) 0.67270(15) 0.49281(4) 0.0256(5) Uani 1 1 d . . . . .
O4 O 0.43047(13) 0.65370(13) 0.46968(4) 0.0162(4) Uani 1 1 d . . . . .
O5 O 0.6667 0.3333 0.49576(6) 0.0136(6) Uani 1 3 d S T P . .
N1 N 0.38406(16) 0.50341(16) 0.36337(4) 0.0180(5) Uani 1 1 d . . . . .
N2 N 0.3354(3) 0.2853(2) 0.35957(6) 0.0559(12) Uani 1 1 d . . . . .
H2B H 0.3395 0.2470 0.3686 0.067 Uiso 1 1 d R U . . .
H2C H 0.3129 0.2718 0.3447 0.067 Uiso 1 1 d R U . . .
C1 C 0.5436(2) 0.47475(19) 0.45759(5) 0.0221(6) Uani 1 1 d . . . . .
C2 C 0.53728(18) 0.53550(18) 0.47066(5) 0.0191(6) Uani 1 1 d . . . . .
H2A H 0.5623 0.5514 0.4862 0.023 Uiso 1 1 calc R U . . .
C3 C 0.49498(18) 0.57302(18) 0.46129(5) 0.0184(6) Uani 1 1 d . . . . .
C4 C 0.45904(18) 0.55064(18) 0.43838(5) 0.0183(5) Uani 1 1 d . . . . .
H4A H 0.4299 0.5765 0.4320 0.022 Uiso 1 1 calc R U . . .
C5 C 0.46550(19) 0.49105(19) 0.42491(5) 0.0213(6) Uani 1 1 d . . . . .
C6 C 0.5078(2) 0.45277(19) 0.43457(5) 0.0241(6) Uani 1 1 d . . . . .
H6A H 0.5123 0.4116 0.4255 0.029 Uiso 1 1 calc R U . . .
C7 C 0.5922(2) 0.43573(19) 0.46790(5) 0.0224(6) Uani 1 1 d . . . . .
C8 C 0.48779(18) 0.63750(17) 0.47594(5) 0.0167(5) Uani 1 1 d . . . . .
C9 C 0.42708(19) 0.46619(19) 0.40038(5) 0.0208(6) Uani 1 1 d . . . . .
C10 C 0.3998(2) 0.3863(2) 0.39167(6) 0.0287(7) Uani 1 1 d . . . . .
H10A H 0.4053 0.3467 0.4013 0.034 Uiso 1 1 calc R U . . .
C11 C 0.3644(2) 0.3645(2) 0.36865(6) 0.0315(8) Uani 1 1 d . . . . .
C12 C 0.3597(2) 0.42607(18) 0.35491(5) 0.0239(6) Uani 1 1 d . . . . .
H12A H 0.3383 0.4126 0.3389 0.029 Uiso 1 1 calc R U . . .
C13 C 0.41715(18) 0.52233(18) 0.38576(5) 0.0177(6) Uani 1 1 d . . . . .
H13A H 0.4346 0.5766 0.3919 0.021 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 O5 1.928(3) . ?
Cu1 O1W 1.942(5) . ?
Cu1 O1 1.995(2) 2_655 ?
Cu1 O1 1.995(2) 3_665 ?
Cu1 O1 1.995(2) . ?
Cu2 O2 1.951(2) . ?
Cu2 O4 1.9700(19) 21_656 ?
Cu2 O5 1.9757(13) . ?
Cu2 N1 2.090(2) 36 ?
Cu2 O4 2.409(2) 19_666 ?
O1 C7 1.242(4) . ?
O2 C7 1.259(3) . ?
O3 C8 1.234(4) . ?
O4 C8 1.285(4) . ?
O4 Cu2 1.9701(19) 20_566 ?
O4 Cu2 2.409(2) 19_666 ?
O5 Cu2 1.9756(13) 3_665 ?
O5 Cu2 1.9756(13) 2_655 ?
N1 C12 1.350(4) . ?
N1 C13 1.347(3) . ?
N1 Cu2 2.090(2) 30_455 ?
N2 C11 1.377(4) . ?
N2 H2B 0.9004 . ?
N2 H2C 0.8995 . ?
C1 C2 1.388(4) . ?
C1 C6 1.398(4) . ?
C1 C7 1.516(4) . ?
C2 C3 1.380(4) . ?
C2 H2A 0.9500 . ?
C3 C4 1.393(4) . ?
C3 C8 1.501(4) . ?
C4 C5 1.384(4) . ?
C4 H4A 0.9500 . ?
C5 C6 1.397(4) . ?
C5 C9 1.492(4) . ?
C6 H6A 0.9500 . ?
C9 C10 1.387(4) . ?
C9 C13 1.398(4) . ?
C10 C11 1.395(4) . ?
C10 H10A 0.9500 . ?
C11 C12 1.408(4) . ?
C12 H12A 0.9500 . ?
C13 H13A 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
O5 Cu1 O1W 180.0 . . ?
O5 Cu1 O1 95.90(8) . 2_655 ?
O1W Cu1 O1 84.10(8) . 2_655 ?
O5 Cu1 O1 95.90(9) . 3_665 ?
O1W Cu1 O1 84.10(8) . 3_665 ?
O1 Cu1 O1 118.96(3) 2_655 3_665 ?
O5 Cu1 O1 95.89(8) . . ?
O1W Cu1 O1 84.11(8) . . ?
O1 Cu1 O1 118.96(3) 2_655 . ?
O1 Cu1 O1 118.96(3) 3_665 . ?
O2 Cu2 O4 169.62(9) . 21_656 ?
O2 Cu2 O5 96.26(9) . . ?
O4 Cu2 O5 86.88(8) 21_656 . ?
O2 Cu2 N1 88.52(9) . 36 ?
O4 Cu2 N1 89.96(9) 21_656 36 ?
O5 Cu2 N1 170.01(10) . 36 ?
O2 Cu2 O4 91.54(9) . 19_666 ?
O4 Cu2 O4 98.83(11) 21_656 19_666 ?
O5 Cu2 O4 75.73(7) . 19_666 ?
N1 Cu2 O4 95.43(8) 36 19_666 ?
C7 O1 Cu1 123.2(2) . . ?
C7 O2 Cu2 134.67(19) . . ?
C8 O4 Cu2 107.19(17) . 20_566 ?
C8 O4 Cu2 108.18(17) . 19_666 ?
Cu2 O4 Cu2 91.31(7) 20_566 19_666 ?
Cu1 O5 Cu2 113.13(8) . 3_665 ?
Cu1 O5 Cu2 113.13(8) . 2_655 ?
Cu2 O5 Cu2 105.58(10) 3_665 2_655 ?
Cu1 O5 Cu2 113.13(8) . . ?
Cu2 O5 Cu2 105.58(10) 3_665 . ?
Cu2 O5 Cu2 105.58(10) 2_655 . ?
C12 N1 C13 117.5(2) . . ?
C12 N1 Cu2 120.63(18) . 30_455 ?
C13 N1 Cu2 121.77(19) . 30_455 ?
C11 N2 H2B 119.4 . . ?
C11 N2 H2C 120.6 . . ?
H2B N2 H2C 120.0 . . ?
C2 C1 C6 119.3(3) . . ?
C2 C1 C7 119.9(3) . . ?
C6 C1 C7 120.7(3) . . ?
C3 C2 C1 120.7(2) . . ?
C3 C2 H2A 119.7 . . ?
C1 C2 H2A 119.7 . . ?
C2 C3 C4 119.8(3) . . ?
C2 C3 C8 119.7(2) . . ?
C4 C3 C8 120.5(3) . . ?
C5 C4 C3 120.5(3) . . ?
C5 C4 H4A 119.8 . . ?
C3 C4 H4A 119.8 . . ?
C4 C5 C6 119.4(3) . . ?
C4 C5 C9 121.1(3) . . ?
C6 C5 C9 119.5(3) . . ?
C5 C6 C1 120.3(3) . . ?
C5 C6 H6A 119.9 . . ?
C1 C6 H6A 119.9 . . ?
O2 C7 O1 127.8(3) . . ?
O2 C7 C1 115.5(2) . . ?
O1 C7 C1 116.7(3) . . ?
O3 C8 O4 123.6(3) . . ?
O3 C8 C3 119.6(3) . . ?
O4 C8 C3 116.8(2) . . ?
C10 C9 C13 118.5(3) . . ?
C10 C9 C5 120.5(3) . . ?
C13 C9 C5 121.0(3) . . ?
C9 C10 C11 119.5(3) . . ?
C9 C10 H10A 120.2 . . ?
C11 C10 H10A 120.2 . . ?
N2 C11 C12 121.0(3) . . ?
N2 C11 C10 121.1(3) . . ?
C12 C11 C10 117.9(3) . . ?
N1 C12 C11 123.2(2) . . ?
N1 C12 H12A 118.4 . . ?
C11 C12 H12A 118.4 . . ?
N1 C13 C9 123.3(3) . . ?
N1 C13 H13A 118.3 . . ?
C9 C13 H13A 118.3 . . ?

_refine_diff_density_max         0.949
_refine_diff_density_min         -3.245
_refine_diff_density_rms         0.121



_vrf_DIFMN02_d_sq                
;
PROBLEM: The minimum difference density is < -0.1*ZMAX*1.00
RESPONSE: This might be caused by incomplete model 
         in terms of inadequately modelled disorder atoms??
;

_vrf_PLAT098_d_sq                
;
PROBLEM: Large Reported Min.  (Negative) Residual Density      -3.24 eA-3. 
RESPONSE: This might be caused by residual absorption disorder.
;

