# 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_Z
_database_code_depnum_ccdc_archive 'CCDC 1949605'
loop_
_audit_author_name
_audit_author_address
'Qian Wang'
;Shaanxi Normal University
China
;
_audit_update_record             
;
2019-08-27 deposited with the CCDC.	2020-10-09 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT212_Z                   
;
PROBLEM: ADP of Atom C2S       is N.P.D. or (nearly) 2D .     Please Check
RESPONSE: This alert is induced by the disorder of DMA+ in the pore of the compund.
;
_vrf_PLAT215_Z                   
;
PROBLEM: Disordered N2        has ADP max/min Ratio .....        5.0 Note
RESPONSE: These alerts are due to the severe disorder between the - COO group and the tetrazole group.
;
_vrf_PLAT315_Z                   
;
PROBLEM: Singly Bonded Carbon Detected (H-atoms Missing).        C1S Check
RESPONSE: This alert is because the DMA+ in the pore of the compund is disordered.
;
# Added during the CSD deposition process: Tuesday 27 August 2019 09:41 AM
# end Validation Reply Form


_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C34 H7 Cl Cu4 N17 O12'
_chemical_formula_weight         1135.18

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'
Cl Cl 0.1484 0.1585 '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      tetragonal
_space_group_IT_number           139
_space_group_name_H-M_alt        'I 4/m m m'
_space_group_name_Hall           '-I 4 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'
'-x, -y, z'
'-y, x, z'
'y, -x, z'
'-x, y, -z'
'x, -y, -z'
'y, x, -z'
'-y, -x, -z'
'x+1/2, y+1/2, z+1/2'
'-x+1/2, -y+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'y+1/2, -x+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z+1/2'
'y+1/2, x+1/2, -z+1/2'
'-y+1/2, -x+1/2, -z+1/2'
'-x, -y, -z'
'x, y, -z'
'y, -x, -z'
'-y, x, -z'
'x, -y, z'
'-x, y, z'
'-y, -x, z'
'y, x, z'
'-x+1/2, -y+1/2, -z+1/2'
'x+1/2, y+1/2, -z+1/2'
'y+1/2, -x+1/2, -z+1/2'
'-y+1/2, x+1/2, -z+1/2'
'x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, z+1/2'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, x+1/2, z+1/2'

_cell_length_a                   13.3835(5)
_cell_length_b                   13.3835(5)
_cell_length_c                   20.4367(15)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3660.6(4)
_cell_formula_units_Z            2
_cell_measurement_temperature    153(2)
_cell_measurement_reflns_used    4294
_cell_measurement_theta_min      2.93
_cell_measurement_theta_max      24.12

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.030
_exptl_crystal_F_000             1118
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    1.230
_shelx_estimated_absorpt_T_min   0.782
_shelx_estimated_absorpt_T_max   0.837
_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      153(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\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            5856
_diffrn_reflns_av_unetI/netI     0.0197
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.934
_diffrn_reflns_theta_max         24.125
_diffrn_reflns_theta_full        24.125
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measured_fraction_theta_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_point_group_measured_fraction_full 0.978
_reflns_number_total             862
_reflns_number_gt                851
_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    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          SQUEEZE
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1391P)²+52.0246P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         862
_refine_ls_number_parameters     64
_refine_ls_number_restraints     5
_refine_ls_R_factor_all          0.0737
_refine_ls_R_factor_gt           0.0732
_refine_ls_wR_factor_ref         0.2166
_refine_ls_wR_factor_gt          0.2161
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_restrained_S_all      1.075
_refine_ls_shift/su_max          0.001
_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 0.0000 0.19173(9) 0.5000 0.0129(5) Uani 1 4 d S T P . .
Cl1 Cl 0.0000 0.0000 0.5000 0.0417(19) Uani 1 16 d S T P . .
O1W O 0.0000 0.3647(13) 0.5000 0.138(9) Uani 1 4 d S T P . .
O1 O 0.0951(9) 0.2084(6) 0.4266(7) 0.0285(17) Uani 0.5 1 d . . P . .
N1 N 0.1112(12) 0.1845(8) 0.4352(9) 0.0285(17) Uani 0.5 1 d . . P . .
N2 N 0.1199(7) 0.2341(7) 0.3796(4) 0.0285(17) Uani 0.5 1 d . . P . .
C1 C 0.1990(5) 0.1990(5) 0.3428(4) 0.0272(19) Uani 1 2 d S T P . .
C2 C 0.2324(8) 0.2324(8) 0.2824(8) 0.026(4) Uani 0.5 2 d S T P . .
C3 C 0.3135(5) 0.1865(5) 0.2500 0.055(3) Uani 1 2 d S T P . .
C4 C 0.1504(12) 0.2787(12) 0.3076(6) 0.055(3) Uani 0.5 1 d . . P . .
C5 C 0.1664(8) 0.1664(8) 0.4055(8) 0.025(4) Uani 0.5 2 d S T P . .
N1S N 0.0000 0.0000 0.2392(19) 0.055(10) Uani 0.5 8 d S T P . .
H1SA H 0.0000 -0.0603 0.2211 0.066 Uiso 0.125 2 d R U P . .
C1S C 0.0000 0.0000 0.304(2) 0.044(10) Uani 0.5 8 d S T P . .
H1SB H 0.0000 -0.0676 0.3185 0.066 Uiso 0.125 2 d R U P . .
H1SC H 0.0586 0.0338 0.3185 0.066 Uiso 0.0625 1 d R U P . .
H1SD H -0.0586 0.0338 0.3185 0.066 Uiso 0.0625 1 d R U P . .
C2S C 0.0000 0.083(7) 0.204(2) 0.08(4) Uani 0.125 2 d S T P . .
H2SA H 0.0000 0.0613 0.1588 0.121 Uiso 0.125 2 d R U P . .
H2SB H -0.0586 0.1200 0.2130 0.121 Uiso 0.0625 1 d R U P . .
H2SC H 0.0586 0.1200 0.2130 0.121 Uiso 0.0625 1 d 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 1.980(17) 18_556 ?
Cu1 O1 1.980(17) 22 ?
Cu1 O1 1.980(17) . ?
Cu1 O1 1.980(17) 5_556 ?
Cu1 N1 1.99(2) 22 ?
Cu1 N1 1.99(2) 18_556 ?
Cu1 N1 1.99(2) 5_556 ?
Cu1 N1 1.99(2) . ?
Cu1 O1W 2.315(17) . ?
Cu1 Cl1 2.5660(12) . ?
Cl1 Cu1 2.5660(12) 19_556 ?
Cl1 Cu1 2.5660(12) 3 ?
Cl1 Cu1 2.5660(12) 17_556 ?
O1 N2 1.074(19) . ?
O1 C5 1.189(18) . ?
N1 C5 0.99(2) . ?
N1 N2 1.32(2) . ?
N1 N1 1.39(3) 24 ?
N2 C5 1.220(13) . ?
N2 C1 1.381(11) . ?
N2 C4 1.638(15) . ?
C1 N2 1.381(11) 24 ?
C1 C2 1.386(18) . ?
C1 C5 1.42(2) . ?
C1 C4 1.441(15) 24 ?
C1 C4 1.441(15) . ?
C2 C4 1.361(16) . ?
C2 C4 1.361(16) 24 ?
C2 C3 1.412(12) . ?
C2 C3 1.412(12) 25 ?
C2 C2 1.48(3) 25 ?
C3 C4 1.356(13) 24 ?
C3 C4 1.356(13) 25 ?
C3 C2 1.412(12) 25 ?
C4 C3 1.356(13) 25 ?
C5 N1 0.99(2) 24 ?
C5 N2 1.220(13) 24 ?
C5 O1 1.189(18) 24 ?
N1S C1S 1.32(6) . ?
N1S C2S 1.31(8) 3 ?
N1S C2S 1.31(8) 2 ?
N1S C2S 1.31(8) 4 ?
N1S C2S 1.31(8) . ?
C2S C2S 1.56(13) 3 ?
C2S C2S 1.56(13) 4 ?

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 167.0(5) 18_556 22 ?
O1 Cu1 O1 98.5(4) 18_556 . ?
O1 Cu1 O1 80.0(4) 22 . ?
O1 Cu1 O1 80.0(4) 18_556 5_556 ?
O1 Cu1 O1 98.5(4) 22 5_556 ?
O1 Cu1 O1 167.0(5) . 5_556 ?
O1 Cu1 N1 171.2(4) 18_556 22 ?
O1 Cu1 N1 12.3(6) 22 22 ?
O1 Cu1 N1 89.0(3) . 22 ?
O1 Cu1 N1 91.6(3) 5_556 22 ?
O1 Cu1 N1 12.3(6) 18_556 18_556 ?
O1 Cu1 N1 171.2(4) 22 18_556 ?
O1 Cu1 N1 91.6(3) . 18_556 ?
O1 Cu1 N1 89.0(3) 5_556 18_556 ?
N1 Cu1 N1 174.4(6) 22 18_556 ?
O1 Cu1 N1 89.0(3) 18_556 5_556 ?
O1 Cu1 N1 91.6(3) 22 5_556 ?
O1 Cu1 N1 171.2(4) . 5_556 ?
O1 Cu1 N1 12.3(6) 5_556 5_556 ?
N1 Cu1 N1 83.2(6) 22 5_556 ?
N1 Cu1 N1 96.6(6) 18_556 5_556 ?
O1 Cu1 N1 91.6(3) 18_556 . ?
O1 Cu1 N1 89.0(3) 22 . ?
O1 Cu1 N1 12.3(6) . . ?
O1 Cu1 N1 171.2(4) 5_556 . ?
N1 Cu1 N1 96.6(6) 22 . ?
N1 Cu1 N1 83.2(6) 18_556 . ?
N1 Cu1 N1 174.4(6) 5_556 . ?
O1 Cu1 O1W 83.5(3) 18_556 . ?
O1 Cu1 O1W 83.5(3) 22 . ?
O1 Cu1 O1W 83.5(3) . . ?
O1 Cu1 O1W 83.5(3) 5_556 . ?
N1 Cu1 O1W 92.8(3) 22 . ?
N1 Cu1 O1W 92.8(3) 18_556 . ?
N1 Cu1 O1W 92.8(3) 5_556 . ?
N1 Cu1 O1W 92.8(3) . . ?
O1 Cu1 Cl1 96.5(3) 18_556 . ?
O1 Cu1 Cl1 96.5(3) 22 . ?
O1 Cu1 Cl1 96.5(3) . . ?
O1 Cu1 Cl1 96.5(3) 5_556 . ?
N1 Cu1 Cl1 87.2(3) 22 . ?
N1 Cu1 Cl1 87.2(3) 18_556 . ?
N1 Cu1 Cl1 87.2(3) 5_556 . ?
N1 Cu1 Cl1 87.2(3) . . ?
O1W Cu1 Cl1 180.0 . . ?
Cu1 Cl1 Cu1 180.0 19_556 3 ?
Cu1 Cl1 Cu1 90.0 19_556 17_556 ?
Cu1 Cl1 Cu1 90.0 3 17_556 ?
Cu1 Cl1 Cu1 90.0 19_556 . ?
Cu1 Cl1 Cu1 90.0 3 . ?
Cu1 Cl1 Cu1 180.0 17_556 . ?
N2 O1 C5 65.0(14) . . ?
N2 O1 Cu1 156.0(10) . . ?
C5 O1 Cu1 137.5(11) . . ?
C5 N1 N2 61.8(13) . . ?
C5 N1 N1 45.3(11) . 24 ?
N2 N1 N1 107.0(9) . 24 ?
C5 N1 Cu1 168.4(13) . . ?
N2 N1 Cu1 127.8(11) . . ?
N1 N1 Cu1 124.2(4) 24 . ?
O1 N2 C5 62.0(11) . . ?
O1 N2 N1 16.6(14) . . ?
C5 N2 N1 45.4(11) . . ?
O1 N2 C1 128.0(11) . . ?
C5 N2 C1 66.0(9) . . ?
N1 N2 C1 111.4(11) . . ?
O1 N2 C4 175.7(12) . . ?
C5 N2 C4 122.2(11) . . ?
N1 N2 C4 167.6(13) . . ?
C1 N2 C4 56.2(7) . . ?
N2 C1 N2 103.0(9) . 24 ?
N2 C1 C2 128.5(5) . . ?
N2 C1 C2 128.5(5) 24 . ?
N2 C1 C5 51.6(5) . . ?
N2 C1 C5 51.6(5) 24 . ?
C2 C1 C5 178.7(11) . . ?
N2 C1 C4 172.9(10) . 24 ?
N2 C1 C4 71.0(6) 24 24 ?
C2 C1 C4 57.5(6) . 24 ?
C5 C1 C4 122.5(6) . 24 ?
N2 C1 C4 71.0(6) . . ?
N2 C1 C4 172.9(10) 24 . ?
C2 C1 C4 57.5(6) . . ?
C5 C1 C4 122.5(6) . . ?
C4 C1 C4 114.8(12) 24 . ?
C4 C2 C4 126.2(16) . 24 ?
C4 C2 C1 63.3(8) . . ?
C4 C2 C1 63.3(8) 24 . ?
C4 C2 C3 174.2(13) . . ?
C4 C2 C3 58.5(6) 24 . ?
C1 C2 C3 121.7(6) . . ?
C4 C2 C3 58.5(6) . 25 ?
C4 C2 C3 174.2(13) 24 25 ?
C1 C2 C3 121.7(6) . 25 ?
C3 C2 C3 116.6(11) . 25 ?
C4 C2 C2 116.7(8) . 25 ?
C4 C2 C2 116.7(8) 24 25 ?
C1 C2 C2 180(2) . 25 ?
C3 C2 C2 58.3(6) . 25 ?
C3 C2 C2 58.3(6) 25 25 ?
C4 C3 C4 178.9(16) 24 25 ?
C4 C3 C2 122.2(11) 24 25 ?
C4 C3 C2 58.9(9) 25 25 ?
C4 C3 C2 58.9(9) 24 . ?
C4 C3 C2 122.2(11) 25 . ?
C2 C3 C2 63.4(11) 25 . ?
C3 C4 C2 62.6(10) 25 . ?
C3 C4 C1 121.8(12) 25 . ?
C2 C4 C1 59.2(9) . . ?
C3 C4 N2 173.5(13) 25 . ?
C2 C4 N2 112.0(11) . . ?
C1 C4 N2 52.8(6) . . ?
N1 C5 N1 89(2) . 24 ?
N1 C5 N2 161.5(17) . 24 ?
N1 C5 N2 72.8(9) 24 24 ?
N1 C5 N2 72.8(9) . . ?
N1 C5 N2 161.6(17) 24 . ?
N2 C5 N2 124.7(17) 24 . ?
N1 C5 O1 19.8(12) . . ?
N1 C5 O1 109.1(17) 24 . ?
N2 C5 O1 174.3(16) 24 . ?
N2 C5 O1 52.9(8) . . ?
N1 C5 O1 109.1(17) . 24 ?
N1 C5 O1 19.8(12) 24 24 ?
N2 C5 O1 52.9(8) 24 24 ?
N2 C5 O1 174.3(16) . 24 ?
O1 C5 O1 129(2) . 24 ?
N1 C5 C1 135.2(11) . . ?
N1 C5 C1 135.2(11) 24 . ?
N2 C5 C1 62.4(9) 24 . ?
N2 C5 C1 62.4(9) . . ?
O1 C5 C1 115.4(10) . . ?
O1 C5 C1 115.4(10) 24 . ?
C1S N1S C2S 123(4) . 3 ?
C1S N1S C2S 123(4) . 2 ?
C2S N1S C2S 73(3) 3 2 ?
C1S N1S C2S 123(4) . 4 ?
C2S N1S C2S 114(7) 3 4 ?
C2S N1S C2S 73(3) 2 4 ?
C1S N1S C2S 123(4) . . ?
C2S N1S C2S 73(3) 3 . ?
C2S N1S C2S 114(7) 2 . ?
C2S N1S C2S 73(3) 4 . ?
N1S C2S C2S 53.5(17) . 3 ?
N1S C2S C2S 53.5(17) . 4 ?
C2S C2S C2S 89.999(6) 3 4 ?

_refine_diff_density_max         2.504
_refine_diff_density_min         -0.708
_refine_diff_density_rms         0.150



_chemical_properties_physical    Moisture-sensitive
