# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 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-7
_database_code_depnum_ccdc_archive 'CCDC 2032687'
loop_
_audit_author_name
_audit_author_address
'Yabing He'
;Zhejiang Normal University
China
;
_audit_update_record             
;
2020-10-06 deposited with the CCDC.	2020-12-16 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         '[Cu4L3Cl]Cl.2.7DMF'
_chemical_formula_sum            'C44.10 H36.90 Cl2 Cu4 N8.70 O14.70'
_chemical_formula_weight         1248.98

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           166
_space_group_name_H-M_alt        'R -3 m :H'
_space_group_name_Hall           '-R 3 2"'

_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'
'x-y, -y, -z'
'-x, -x+y, -z'
'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+1/3'
'x-y+2/3, -y+1/3, -z+1/3'
'-x+2/3, -x+y+1/3, -z+1/3'
'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+2/3'
'x-y+1/3, -y+2/3, -z+2/3'
'-x+1/3, -x+y+2/3, -z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'-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+1/3'
'-x+y+2/3, y+1/3, z+1/3'
'x+2/3, x-y+1/3, z+1/3'
'-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+2/3'
'-x+y+1/3, y+2/3, z+2/3'
'x+1/3, x-y+2/3, z+2/3'

_cell_length_a                   18.6356(4)
_cell_length_b                   18.6356(4)
_cell_length_c                   28.6177(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     8607.0(4)
_cell_formula_units_Z            6
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    17790
_cell_measurement_theta_min      3.0
_cell_measurement_theta_max      27.5

_exptl_crystal_description       block
_exptl_crystal_colour            blue
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_F_000             3780
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.130
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    1.621
_shelx_estimated_absorpt_T_min   0.781
_shelx_estimated_absorpt_T_max   0.855
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.777
_exptl_absorpt_correction_T_max  0.850
_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            17790
_diffrn_reflns_av_unetI/netI     0.0165
_diffrn_reflns_av_R_equivalents  0.0289
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_theta_min         3.056
_diffrn_reflns_theta_max         27.490
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measured_fraction_theta_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.992
_reflns_number_total             2392
_reflns_number_gt                2178
_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)+(0.1450P)²] 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         2392
_refine_ls_number_parameters     106
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0379
_refine_ls_wR_factor_ref         0.1661
_refine_ls_wR_factor_gt          0.1600
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_restrained_S_all      1.045
_refine_ls_shift/su_max          0.014
_refine_ls_shift/su_mean         0.003

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 0.52326(2) 0.47674(2) 0.53766(2) 0.0182(2) Uani 1 2 d S T P . .
Cu2 Cu 0.0000 0.0000 0.34649(2) 0.0285(2) Uani 1 6 d S T P . .
Cl1 Cl 0.0000 0.0000 0.42823(5) 0.0398(4) Uani 1 6 d S T P . .
O2 O 0.44065(12) 0.40910(11) 0.44203(6) 0.0317(4) Uani 1 1 d . . . . .
O1 O 0.48240(12) 0.37084(11) 0.50608(6) 0.0327(4) Uani 1 1 d . . . . .
N1 N 0.23125(17) 0.11562(9) 0.27436(9) 0.0260(6) Uani 1 2 d S T P . .
N2 N 0.12323(18) 0.06161(9) 0.32969(9) 0.0289(6) Uani 1 2 d S T P . .
C6 C 0.2650(2) 0.13250(11) 0.35478(11) 0.0252(6) Uani 1 2 d S T P . .
C1 C 0.44931(15) 0.35761(14) 0.46630(8) 0.0249(5) Uani 1 1 d . . . . .
C7 C 0.28726(19) 0.14363(10) 0.30846(12) 0.0286(8) Uani 1 2 d S T P . .
H7A H 0.3444 0.1722 0.3005 0.034 Uiso 1 2 calc R U P . .
C5 C 0.3293(2) 0.16466(10) 0.39269(10) 0.0258(6) Uani 1 2 d S T P . .
C3 C 0.4450(2) 0.22250(10) 0.46467(10) 0.0248(6) Uani 1 2 d S T P . .
H3A H 0.4834 0.2417 0.4898 0.030 Uiso 1 2 calc R U P . .
C2 C 0.41728(15) 0.27311(15) 0.44649(8) 0.0257(5) Uani 1 1 d . . . . .
C4 C 0.35881(16) 0.24406(15) 0.41025(8) 0.0279(5) Uani 1 1 d . . . . .
H4A H 0.3394 0.2785 0.3977 0.033 Uiso 1 1 calc R U . . .
C8 C 0.1520(2) 0.07599(11) 0.28603(12) 0.0292(7) Uani 1 2 d S T P . .
H8A H 0.1125 0.0563 0.2614 0.035 Uiso 1 2 calc R U P . .
C9 C 0.1802(2) 0.09008(11) 0.36386(12) 0.0307(7) Uani 1 2 d S T P . .
H9A H 0.1620 0.0810 0.3954 0.037 Uiso 1 2 calc R U 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
Cu1 O1 1.9465(17) 22_665 ?
Cu1 O1 1.9465(17) . ?
Cu1 O2 1.9711(17) 19_666 ?
Cu1 O2 1.9711(17) 4_556 ?
Cu1 N1 2.196(3) 8 ?
Cu1 Cu1 2.6266(6) 19_666 ?
Cu2 N2 2.046(3) 2 ?
Cu2 N2 2.046(3) . ?
Cu2 N2 2.046(3) 3 ?
Cu2 Cl1 2.3392(16) . ?
O2 C1 1.259(3) . ?
O2 Cu1 1.9710(17) 19_666 ?
O1 C1 1.259(3) . ?
N1 C8 1.322(5) . ?
N1 C7 1.330(4) . ?
N1 Cu1 2.196(3) 15_554 ?
N2 C9 1.342(4) . ?
N2 C8 1.333(4) . ?
C6 C7 1.373(5) . ?
C6 C9 1.393(5) . ?
C6 C5 1.502(4) . ?
C1 C2 1.489(3) . ?
C7 H7A 0.9500 . ?
C5 C4 1.390(3) . ?
C5 C4 1.389(3) 24 ?
C3 C2 1.384(3) 24 ?
C3 C2 1.384(3) . ?
C3 H3A 0.9500 . ?
C2 C4 1.402(3) . ?
C4 H4A 0.9500 . ?
C8 H8A 0.9500 . ?
C9 H9A 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
O1 Cu1 O1 89.26(12) 22_665 . ?
O1 Cu1 O2 89.01(9) 22_665 19_666 ?
O1 Cu1 O2 168.71(7) . 19_666 ?
O1 Cu1 O2 168.71(7) 22_665 4_556 ?
O1 Cu1 O2 89.01(9) . 4_556 ?
O2 Cu1 O2 90.51(12) 19_666 4_556 ?
O1 Cu1 N1 101.74(7) 22_665 8 ?
O1 Cu1 N1 101.74(7) . 8 ?
O2 Cu1 N1 89.53(7) 19_666 8 ?
O2 Cu1 N1 89.53(7) 4_556 8 ?
O1 Cu1 Cu1 85.83(5) 22_665 19_666 ?
O1 Cu1 Cu1 85.83(5) . 19_666 ?
O2 Cu1 Cu1 82.92(5) 19_666 19_666 ?
O2 Cu1 Cu1 82.92(5) 4_556 19_666 ?
N1 Cu1 Cu1 169.25(8) 8 19_666 ?
N2 Cu2 N2 114.66(6) 2 . ?
N2 Cu2 N2 114.66(6) 2 3 ?
N2 Cu2 N2 114.66(6) . 3 ?
N2 Cu2 Cl1 103.59(8) 2 . ?
N2 Cu2 Cl1 103.58(8) . . ?
N2 Cu2 Cl1 103.58(8) 3 . ?
C1 O2 Cu1 123.74(15) . 19_666 ?
C1 O1 Cu1 121.56(15) . . ?
C8 N1 C7 118.2(3) . . ?
C8 N1 Cu1 128.7(2) . 15_554 ?
C7 N1 Cu1 113.1(2) . 15_554 ?
C9 N2 C8 116.4(3) . . ?
C9 N2 Cu2 119.6(2) . . ?
C8 N2 Cu2 124.0(2) . . ?
C7 C6 C9 115.9(3) . . ?
C7 C6 C5 121.1(3) . . ?
C9 C6 C5 123.0(3) . . ?
O2 C1 O1 125.9(2) . . ?
O2 C1 C2 117.36(19) . . ?
O1 C1 C2 116.7(2) . . ?
N1 C7 C6 122.0(3) . . ?
N1 C7 H7A 119.0 . . ?
C6 C7 H7A 119.0 . . ?
C4 C5 C4 120.3(3) . 24 ?
C4 C5 C6 119.87(15) . . ?
C4 C5 C6 119.87(15) 24 . ?
C2 C3 C2 120.5(3) 24 . ?
C2 C3 H3A 119.7 24 . ?
C2 C3 H3A 119.7 . . ?
C3 C2 C4 119.9(2) . . ?
C3 C2 C1 119.3(2) . . ?
C4 C2 C1 120.9(2) . . ?
C5 C4 C2 119.7(2) . . ?
C5 C4 H4A 120.1 . . ?
C2 C4 H4A 120.1 . . ?
N1 C8 N2 125.0(3) . . ?
N1 C8 H8A 117.5 . . ?
N2 C8 H8A 117.5 . . ?
N2 C9 C6 122.5(3) . . ?
N2 C9 H9A 118.8 . . ?
C6 C9 H9A 118.8 . . ?

_refine_diff_density_max         0.641
_refine_diff_density_min         -1.848
_refine_diff_density_rms         0.089




