# Electronic Supplementary Material (ESI) for Analytical Methods.
# 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_7
_database_code_depnum_ccdc_archive 'CCDC 2099386'
loop_
_audit_author_name
_audit_author_address
'Boya Su'
;Tianjin University of Technology
China
;
_audit_update_record             
;
2021-07-26 deposited with the CCDC.	2021-11-05 downloaded from the CCDC.
;
_audit_creation_date             2021-03-29
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        Zn-4py-ligand
_chemical_formula_moiety         'C88 H44 N16 O16 Zn4, 4(H2 O)'
_chemical_formula_sum            'C88 H56 N16 O20 Zn4'
_chemical_formula_weight         1918.96
_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'
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'
Zn Zn 0.2839 1.4301 '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           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   7.9231(4)
_cell_length_b                   13.8107(6)
_cell_length_c                   17.1406(8)
_cell_angle_alpha                90
_cell_angle_beta                 102.171(5)
_cell_angle_gamma                90
_cell_volume                     1833.43(15)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    3738
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      32.6620
_cell_measurement_theta_min      2.9730
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    1.388
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37117
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.7e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            ?
_exptl_crystal_density_diffrn    1.738
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.18
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0416
_diffrn_reflns_av_unetI/netI     0.0740
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.880
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            10152
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.880
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.092
_diffrn_reflns_theta_min         3.015
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.880
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω      4.00  30.00   1.00    6.42    --   30.00  54.00  60.00   26
  2  ω    -58.00 118.00   1.00    6.42    --   30.00  54.00-180.00  176
  3  ω    -71.00 -46.00   1.00    6.42    --   30.00  54.00  60.00   25
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini (ROW)'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0773637000
_diffrn_orient_matrix_UB_12      0.0270858000
_diffrn_orient_matrix_UB_13      -0.0111312000
_diffrn_orient_matrix_UB_21      0.0487720000
_diffrn_orient_matrix_UB_22      0.0434689000
_diffrn_orient_matrix_UB_23      0.0038710000
_diffrn_orient_matrix_UB_31      0.0057160000
_diffrn_orient_matrix_UB_32      -0.0033413000
_diffrn_orient_matrix_UB_33      -0.0406618000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4281
_reflns_number_total             6132
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.636
_refine_diff_density_min         -0.854
_refine_diff_density_rms         0.106
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.777
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         6132
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0728
_refine_ls_R_factor_gt           0.0403
_refine_ls_restrained_S_all      0.777
_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)+(0.0897P)²+0.7720P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1035
_refine_ls_wR_factor_ref         0.1328
_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,H) groups
2.a Free rotating group:
 O5(H5a,H5b)
2.b Aromatic/amide H refined with riding coordinates:
 C15(H15), C13(H13), C10(H10), C16(H16), C8(H8), C4(H4), C5(H5), C19(H19),
 C21(H21), C22(H22), C20(H20)
;
_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
Zn1 Zn 0.70266(3) 0.55219(2) 0.12559(2) 0.01950(9) Uani 1 1 d . . . . .
O2 O 0.5754(2) 0.44355(11) 0.16068(11) 0.0261(3) Uani 1 1 d . . . . .
O3 O -0.0738(2) -0.05223(12) 0.70390(10) 0.0287(4) Uani 1 1 d . . . . .
N2 N 0.3065(2) 0.18743(13) 0.42881(10) 0.0212(4) Uani 1 1 d . . . . .
N1 N 0.4258(2) 0.14952(13) 0.30334(11) 0.0216(4) Uani 1 1 d . . . . .
N3 N 0.2527(2) 0.02232(13) 0.49202(10) 0.0208(4) Uani 1 1 d . . . . .
O4 O 0.1678(3) 0.01296(18) 0.77190(10) 0.0443(5) Uani 1 1 d . . . . .
O1 O 0.7622(3) 0.33191(15) 0.13840(13) 0.0436(5) Uani 1 1 d . . . . .
O5 O 1.0507(3) 0.21073(17) 0.18875(15) 0.0538(6) Uani 1 1 d . . . . .
H5A H 0.9560 0.2396 0.1888 0.081 Uiso 1 1 d G . . . .
H5B H 1.0500 0.1622 0.2191 0.081 Uiso 1 1 d G . . . .
C11 C 0.2526(3) 0.19570(15) 0.49760(12) 0.0199(4) Uani 1 1 d . . . . .
C2 C 0.5568(3) 0.28622(15) 0.21345(12) 0.0212(4) Uani 1 1 d . . . . .
C12 C 0.2234(3) 0.10100(16) 0.53381(12) 0.0192(4) Uani 1 1 d . . . . .
C14 C 0.1365(3) 0.00199(16) 0.63316(12) 0.0196(4) Uani 1 1 d . . . . .
C15 C 0.1700(3) -0.07925(17) 0.59058(13) 0.0248(4) Uani 1 1 d . . . . .
H15 H 0.1525 -0.1413 0.6084 0.030 Uiso 1 1 calc R . . . .
C13 C 0.1671(3) 0.09351(16) 0.60497(12) 0.0196(4) Uani 1 1 d . . . . .
H13 H 0.1500 0.1488 0.6334 0.024 Uiso 1 1 calc R . . . .
C7 C 0.3439(3) 0.26613(16) 0.39046(12) 0.0206(4) Uani 1 1 d . . . . .
C6 C 0.4141(3) 0.24446(15) 0.31857(12) 0.0197(4) Uani 1 1 d . . . . .
C10 C 0.2302(3) 0.28610(16) 0.52973(13) 0.0236(4) Uani 1 1 d . . . . .
H10 H 0.1931 0.2909 0.5776 0.028 Uiso 1 1 calc R . . . .
C3 C 0.4729(3) 0.31518(16) 0.27301(13) 0.0220(4) Uani 1 1 d . . . . .
C17 C 0.0734(3) -0.01070(16) 0.70956(12) 0.0218(4) Uani 1 1 d . . . . .
C16 C 0.2299(3) -0.06513(16) 0.52101(14) 0.0251(5) Uani 1 1 d . . . . .
H16 H 0.2553 -0.1192 0.4933 0.030 Uiso 1 1 calc R . . . .
C8 C 0.3229(3) 0.35835(16) 0.41909(13) 0.0248(4) Uani 1 1 d . . . . .
H8 H 0.3483 0.4124 0.3914 0.030 Uiso 1 1 calc R . . . .
N4 N 0.1798(3) 0.65605(17) 0.57533(15) 0.0400(5) Uani 1 1 d . . . . .
C4 C 0.5733(3) 0.18789(17) 0.19956(14) 0.0281(5) Uani 1 1 d . . . . .
H4 H 0.6309 0.1666 0.1608 0.034 Uiso 1 1 calc R . . . .
C1 C 0.6395(3) 0.35839(16) 0.16664(13) 0.0235(4) Uani 1 1 d . . . . .
C18 C 0.2358(3) 0.46793(17) 0.51959(14) 0.0251(4) Uani 1 1 d . . . . .
C9 C 0.2636(3) 0.36960(16) 0.48964(13) 0.0224(4) Uani 1 1 d . . . . .
C5 C 0.5022(3) 0.12207(17) 0.24467(14) 0.0262(5) Uani 1 1 d . . . . .
H5 H 0.5081 0.0564 0.2336 0.031 Uiso 1 1 calc R . . . .
C19 C 0.1934(4) 0.4829(2) 0.59369(15) 0.0341(6) Uani 1 1 d . . . . .
H19 H 0.1833 0.4306 0.6266 0.041 Uiso 1 1 calc R . . . .
C21 C 0.2428(5) 0.55053(18) 0.47370(19) 0.0420(7) Uani 1 1 d . . . . .
H21 H 0.2651 0.5451 0.4227 0.050 Uiso 1 1 calc R . . . .
C22 C 0.2162(5) 0.6412(2) 0.50455(19) 0.0465(7) Uani 1 1 d . . . . .
H22 H 0.2248 0.6951 0.4731 0.056 Uiso 1 1 calc R . . . .
C20 C 0.1664(4) 0.5766(2) 0.61793(17) 0.0391(6) Uani 1 1 d . . . . .
H20 H 0.1370 0.5845 0.6673 0.047 Uiso 1 1 calc R . . . .


_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
Zn1 O2 1.9711(16) . ?
Zn1 O3 1.9840(17) 4_665 ?
Zn1 N2 2.0821(18) 2_655 ?
Zn1 N1 2.2020(18) 2_655 ?
Zn1 N3 2.1589(18) 2_655 ?
O2 C1 1.277(3) . ?
O3 Zn1 1.9839(17) 4_466 ?
O3 C17 1.285(3) . ?
N2 Zn1 2.0821(18) 2_645 ?
N2 C11 1.341(3) . ?
N2 C7 1.336(3) . ?
N1 Zn1 2.2019(18) 2_645 ?
N1 C6 1.344(3) . ?
N1 C5 1.334(3) . ?
N3 Zn1 2.1590(18) 2_645 ?
N3 C12 1.348(3) . ?
N3 C16 1.333(3) . ?
O4 C17 1.213(3) . ?
O1 C1 1.230(3) . ?
O5 H5A 0.8497 . ?
O5 H5B 0.8496 . ?
C11 C12 1.486(3) . ?
C11 C10 1.391(3) . ?
C2 C3 1.389(3) . ?
C2 C4 1.390(3) . ?
C2 C1 1.513(3) . ?
C12 C13 1.388(3) . ?
C14 C15 1.394(3) . ?
C14 C13 1.393(3) . ?
C14 C17 1.507(3) . ?
C15 H15 0.9300 . ?
C15 C16 1.387(3) . ?
C13 H13 0.9300 . ?
C7 C6 1.485(3) . ?
C7 C8 1.387(3) . ?
C6 C3 1.391(3) . ?
C10 H10 0.9300 . ?
C10 C9 1.396(3) . ?
C16 H16 0.9300 . ?
C8 H8 0.9300 . ?
C8 C9 1.395(3) . ?
N4 C22 1.321(4) . ?
N4 C20 1.334(4) . ?
C4 H4 0.9300 . ?
C4 C5 1.387(3) . ?
C18 C9 1.485(3) . ?
C18 C19 1.396(3) . ?
C18 C21 1.393(3) . ?
C5 H5 0.9300 . ?
C19 H19 0.9300 . ?
C19 C20 1.390(4) . ?
C21 H21 0.9300 . ?
C21 C22 1.392(4) . ?
C22 H22 0.9300 . ?
C20 H20 0.9300 . ?

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
O2 Zn1 O3 103.59(8) . 4_665 ?
O2 Zn1 N2 147.97(7) . 2_655 ?
O2 Zn1 N1 88.29(7) . 2_655 ?
O2 Zn1 N3 109.55(7) . 2_655 ?
O3 Zn1 N2 104.15(8) 4_665 2_655 ?
O3 Zn1 N1 94.38(7) 4_665 2_655 ?
O3 Zn1 N3 109.45(7) 4_665 2_655 ?
N2 Zn1 N1 73.96(7) 2_655 2_655 ?
N2 Zn1 N3 75.54(7) 2_655 2_655 ?
N3 Zn1 N1 145.00(7) 2_655 2_655 ?
C1 O2 Zn1 120.34(15) . . ?
C17 O3 Zn1 135.86(15) . 4_466 ?
C11 N2 Zn1 118.87(14) . 2_645 ?
C7 N2 Zn1 119.99(14) . 2_645 ?
C7 N2 C11 120.56(18) . . ?
C6 N1 Zn1 115.42(14) . 2_645 ?
C5 N1 Zn1 125.44(15) . 2_645 ?
C5 N1 C6 119.00(19) . . ?
C12 N3 Zn1 114.99(14) . 2_645 ?
C16 N3 Zn1 125.67(14) . 2_645 ?
C16 N3 C12 118.72(18) . . ?
H5A O5 H5B 104.5 . . ?
N2 C11 C12 113.48(18) . . ?
N2 C11 C10 121.03(19) . . ?
C10 C11 C12 125.48(18) . . ?
C3 C2 C1 121.9(2) . . ?
C4 C2 C3 118.9(2) . . ?
C4 C2 C1 119.08(19) . . ?
N3 C12 C11 115.36(18) . . ?
N3 C12 C13 121.99(19) . . ?
C13 C12 C11 122.64(19) . . ?
C15 C14 C17 119.72(19) . . ?
C13 C14 C15 118.87(19) . . ?
C13 C14 C17 121.39(19) . . ?
C14 C15 H15 120.8 . . ?
C16 C15 C14 118.3(2) . . ?
C16 C15 H15 120.8 . . ?
C12 C13 C14 119.0(2) . . ?
C12 C13 H13 120.5 . . ?
C14 C13 H13 120.5 . . ?
N2 C7 C6 113.90(18) . . ?
N2 C7 C8 121.16(19) . . ?
C8 C7 C6 124.90(19) . . ?
N1 C6 C7 114.27(18) . . ?
N1 C6 C3 122.08(19) . . ?
C3 C6 C7 123.55(19) . . ?
C11 C10 H10 120.2 . . ?
C11 C10 C9 119.54(19) . . ?
C9 C10 H10 120.2 . . ?
C6 C3 C2 118.6(2) . . ?
O3 C17 C14 116.65(19) . . ?
O4 C17 O3 124.6(2) . . ?
O4 C17 C14 118.6(2) . . ?
N3 C16 C15 123.1(2) . . ?
N3 C16 H16 118.5 . . ?
C15 C16 H16 118.5 . . ?
C7 C8 H8 120.1 . . ?
C7 C8 C9 119.7(2) . . ?
C9 C8 H8 120.1 . . ?
C22 N4 C20 115.6(2) . . ?
C2 C4 H4 120.6 . . ?
C5 C4 C2 118.7(2) . . ?
C5 C4 H4 120.6 . . ?
O2 C1 C2 116.09(19) . . ?
O1 C1 O2 125.2(2) . . ?
O1 C1 C2 118.7(2) . . ?
C19 C18 C9 122.1(2) . . ?
C21 C18 C9 121.8(2) . . ?
C21 C18 C19 116.0(2) . . ?
C10 C9 C8 117.9(2) . . ?
C10 C9 C18 121.9(2) . . ?
C8 C9 C18 120.2(2) . . ?
N1 C5 C4 122.4(2) . . ?
N1 C5 H5 118.8 . . ?
C4 C5 H5 118.8 . . ?
C18 C19 H19 120.3 . . ?
C20 C19 C18 119.4(2) . . ?
C20 C19 H19 120.3 . . ?
C18 C21 H21 120.2 . . ?
C18 C21 C22 119.6(3) . . ?
C22 C21 H21 120.2 . . ?
N4 C22 C21 124.7(3) . . ?
N4 C22 H22 117.7 . . ?
C21 C22 H22 117.7 . . ?
N4 C20 C19 124.6(2) . . ?
N4 C20 H20 117.7 . . ?
C19 C20 H20 117.7 . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.918
_oxdiff_exptl_absorpt_empirical_full_min 0.646
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: H2O'
