# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_31
_database_code_depnum_ccdc_archive 'CCDC 1888675'
loop_
_audit_author_name
_audit_author_address
'Yuan youyou'
;Peking university
China
;
_audit_update_record             
;
2019-02-25 deposited with the CCDC.	2019-03-14 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         ?
_chemical_formula_sum            'H26 N4 O60 V20 Zn5'
_chemical_formula_weight         2387.90

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
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'
V V 0.3005 0.5294 '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'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   10.3342(6)
_cell_length_b                   8.1209(5)
_cell_length_c                   14.7616(9)
_cell_angle_alpha                90
_cell_angle_beta                 102.064(6)
_cell_angle_gamma                90
_cell_volume                     1211.48(13)
_cell_formula_units_Z            1
_cell_measurement_temperature    179.99(10)
_cell_measurement_reflns_used    2053
_cell_measurement_theta_min      3.6840
_cell_measurement_theta_max      27.5220

_exptl_crystal_description       'black butterfly'
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    3.273
_exptl_crystal_F_000             1144
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.001
_exptl_absorpt_coefficient_mu    6.219
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.64499
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;                                                         
CrysAlisPro 1.171.39.9f (Rigaku Oxford Diffraction, 2015) 
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.         
;
_exptl_absorpt_special_details   
; 
 ?
;
_diffrn_ambient_temperature      179.99(10)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.3914
_diffrn_reflns_number            4271
_diffrn_reflns_av_unetI/netI     0.0823
_diffrn_reflns_av_R_equivalents  ?
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         3.680
_diffrn_reflns_theta_max         27.897
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.921
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.921
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             4271
_reflns_number_gt                2811
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 _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       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_structure_solution    'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 Refined as a 2-component twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0573P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4271
_refine_ls_number_parameters     191
_refine_ls_number_restraints     17
_refine_ls_R_factor_all          0.0806
_refine_ls_R_factor_gt           0.0468
_refine_ls_wR_factor_ref         0.1184
_refine_ls_wR_factor_gt          0.1109
_refine_ls_goodness_of_fit_ref   0.973
_refine_ls_restrained_S_all      0.971
_refine_ls_shift/su_max          0.000
_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
Zn1 Zn 0.11761(8) 0.22980(11) 0.11808(6) 0.0077(2) Uani 1 1 d . . . . .
V1 V -0.02278(12) 0.29634(15) -0.17910(9) 0.0068(3) Uani 1 1 d . . . . .
V2 V -0.34037(12) 0.47028(15) -0.17543(8) 0.0069(3) Uani 1 1 d . . . . .
V3 V -0.32014(12) 0.10416(16) -0.16983(9) 0.0067(3) Uani 1 1 d . . . . .
V4 V -0.16008(12) 0.03203(16) 0.04118(8) 0.0069(3) Uani 1 1 d . . . . .
V5 V -0.15548(12) 0.43572(15) 0.00887(9) 0.0066(3) Uani 1 1 d . . . . .
Zn2 Zn -0.5000 0.0000 0.0000 0.0125(6) Uani 0.5 2 d S . P . .
O1 O -0.2254(5) 0.2989(6) -0.1021(3) 0.0090(4) Uani 1 1 d . . . . .
O2 O -0.2971(5) 0.0414(7) 0.0812(4) 0.0153(13) Uani 1 1 d . . . . .
O3 O -0.0720(5) 0.2242(6) 0.0596(3) 0.0081(11) Uani 1 1 d . . . . .
O4 O -0.1492(5) 0.4548(6) -0.2438(3) 0.0090(4) Uani 1 1 d . . . . .
O5 O -0.2720(5) 0.4347(6) 0.0664(4) 0.0110(12) Uani 1 1 d . . . . .
O6 O 0.0294(5) 0.4432(6) -0.0754(3) 0.0090(4) Uani 1 1 d . . . . .
O7 O -0.1372(5) 0.1229(6) -0.2373(3) 0.0090(4) Uani 1 1 d . . . . .
O8 O 0.0631(5) 0.1167(6) -0.0962(3) 0.0090(4) Uani 1 1 d . . . . .
O9 O 0.1981(5) 0.0280(6) 0.0778(3) 0.0090(4) Uani 1 1 d . . . . .
O10 O 0.1123(5) 0.2194(6) 0.2491(3) 0.0090(4) Uani 1 1 d . . . . .
O11 O -0.4713(5) 0.4744(6) -0.1332(4) 0.0123(12) Uani 1 1 d . . . . .
O12 O 0.2263(5) 0.4009(6) 0.0809(3) 0.0075(11) Uani 1 1 d . . . . .
O13 O 0.0881(5) 0.3237(7) -0.2397(4) 0.0142(13) Uani 1 1 d D . . . .
H13A H 0.024(9) 0.379(10) -0.287(8) 0.017 Uiso 0.5 1 d D U P . .
O14 O -0.4429(5) 0.0825(6) -0.1184(3) 0.0092(12) Uani 1 1 d . . . . .
O15 O -0.4526(7) -0.2402(8) -0.0211(5) 0.0345(18) Uani 1 1 d D . . . .
H15A H -0.519(3) -0.326(6) -0.036(5) 0.041 Uiso 1 1 d D U . . .
H15B H -0.376(6) -0.295(11) -0.033(6) 0.041 Uiso 1 1 d D U . . .
N16 N 0.3317(7) 0.1903(10) 0.7561(5) 0.0259(19) Uani 1 1 d D . . . .
HN1 H 0.408(4) 0.249(8) 0.763(5) 0.031 Uiso 1 1 d D U . . .
HN2 H 0.309(7) 0.144(8) 0.699(3) 0.031 Uiso 1 1 d D U . . .
HN3 H 0.268(5) 0.260(7) 0.768(5) 0.031 Uiso 1 1 d D U . . .
HN4 H 0.341(7) 0.105(6) 0.798(4) 0.031 Uiso 1 1 d D 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
Zn1 O12 1.937(5) . ?
Zn1 O10 1.948(5) . ?
Zn1 O3 1.970(5) . ?
Zn1 O9 1.985(5) . ?
V1 O13 1.609(6) . ?
V1 O7 1.922(5) . ?
V1 O6 1.926(5) . ?
V1 O4 1.937(5) . ?
V1 O8 1.990(5) . ?
V2 O11 1.604(5) . ?
V2 O7 1.768(5) 2_454 ?
V2 O10 1.904(5) 4_565 ?
V2 O12 1.935(5) 3_565 ?
V2 O1 1.995(5) . ?
V2 O4 2.403(5) . ?
V3 O14 1.619(5) . ?
V3 O4 1.740(5) 2_444 ?
V3 O10 1.904(5) 4_565 ?
V3 O9 1.967(5) 3 ?
V3 O1 2.012(5) . ?
V3 O7 2.319(6) . ?
V4 O2 1.646(6) . ?
V4 O8 1.668(5) 3 ?
V4 O9 1.786(5) 3 ?
V4 O3 1.799(5) . ?
V5 O5 1.612(5) . ?
V5 O6 1.759(5) 3_565 ?
V5 O12 1.909(5) 3_565 ?
V5 O1 1.986(5) . ?
V5 O3 1.996(5) . ?
Zn2 O15 2.051(6) . ?
Zn2 O15 2.051(6) 3_455 ?
Zn2 O14 2.070(5) . ?
Zn2 O14 2.070(5) 3_455 ?
Zn2 O2 2.212(5) 3_455 ?
Zn2 O2 2.212(5) . ?
O4 V3 1.740(5) 2_454 ?
O6 V5 1.759(5) 3_565 ?
O7 V2 1.768(5) 2_444 ?
O8 V4 1.668(5) 3 ?
O9 V4 1.786(5) 3 ?
O9 V3 1.967(5) 3 ?
O10 V3 1.904(5) 4_666 ?
O10 V2 1.904(5) 4_666 ?
O12 V5 1.909(5) 3_565 ?
O12 V2 1.935(5) 3_565 ?

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
O12 Zn1 O10 116.8(2) . . ?
O12 Zn1 O3 118.4(2) . . ?
O10 Zn1 O3 101.6(2) . . ?
O12 Zn1 O9 101.7(2) . . ?
O10 Zn1 O9 111.2(2) . . ?
O3 Zn1 O9 106.9(2) . . ?
O13 V1 O7 107.2(3) . . ?
O13 V1 O6 104.0(3) . . ?
O7 V1 O6 148.5(2) . . ?
O13 V1 O4 96.9(2) . . ?
O7 V1 O4 88.7(2) . . ?
O6 V1 O4 91.6(2) . . ?
O13 V1 O8 99.5(2) . . ?
O7 V1 O8 83.8(2) . . ?
O6 V1 O8 87.1(2) . . ?
O4 V1 O8 163.4(2) . . ?
O11 V2 O7 106.0(3) . 2_454 ?
O11 V2 O10 96.3(2) . 4_565 ?
O7 V2 O10 99.3(2) 2_454 4_565 ?
O11 V2 O12 98.3(2) . 3_565 ?
O7 V2 O12 96.6(2) 2_454 3_565 ?
O10 V2 O12 154.5(2) 4_565 3_565 ?
O11 V2 O1 105.0(3) . . ?
O7 V2 O1 149.0(2) 2_454 . ?
O10 V2 O1 78.7(2) 4_565 . ?
O12 V2 O1 77.4(2) 3_565 . ?
O11 V2 O4 177.3(2) . . ?
O7 V2 O4 74.0(2) 2_454 . ?
O10 V2 O4 81.1(2) 4_565 . ?
O12 V2 O4 84.31(19) 3_565 . ?
O1 V2 O4 75.1(2) . . ?
O14 V3 O4 103.1(3) . 2_444 ?
O14 V3 O10 99.0(2) . 4_565 ?
O4 V3 O10 94.4(2) 2_444 4_565 ?
O14 V3 O9 94.0(2) . 3 ?
O4 V3 O9 96.8(2) 2_444 3 ?
O10 V3 O9 160.5(2) 4_565 3 ?
O14 V3 O1 101.5(2) . . ?
O4 V3 O1 155.1(2) 2_444 . ?
O10 V3 O1 78.3(2) 4_565 . ?
O9 V3 O1 84.9(2) 3 . ?
O14 V3 O7 176.4(2) . . ?
O4 V3 O7 76.8(2) 2_444 . ?
O10 V3 O7 84.6(2) 4_565 . ?
O9 V3 O7 82.5(2) 3 . ?
O1 V3 O7 78.8(2) . . ?
O2 V4 O8 109.5(3) . 3 ?
O2 V4 O9 109.7(2) . 3 ?
O8 V4 O9 105.5(2) 3 3 ?
O2 V4 O3 110.6(3) . . ?
O8 V4 O3 108.7(2) 3 . ?
O9 V4 O3 112.7(2) 3 . ?
O5 V5 O6 104.8(3) . 3_565 ?
O5 V5 O12 98.6(2) . 3_565 ?
O6 V5 O12 97.5(2) 3_565 3_565 ?
O5 V5 O1 104.4(2) . . ?
O6 V5 O1 150.8(2) 3_565 . ?
O12 V5 O1 78.2(2) 3_565 . ?
O5 V5 O3 96.3(2) . . ?
O6 V5 O3 93.4(2) 3_565 . ?
O12 V5 O3 158.6(2) 3_565 . ?
O1 V5 O3 83.3(2) . . ?
O15 Zn2 O15 180.0 . 3_455 ?
O15 Zn2 O14 93.4(3) . . ?
O15 Zn2 O14 86.6(3) 3_455 . ?
O15 Zn2 O14 86.6(3) . 3_455 ?
O15 Zn2 O14 93.4(3) 3_455 3_455 ?
O14 Zn2 O14 180.0(2) . 3_455 ?
O15 Zn2 O2 90.1(2) . 3_455 ?
O15 Zn2 O2 89.9(2) 3_455 3_455 ?
O14 Zn2 O2 89.8(2) . 3_455 ?
O14 Zn2 O2 90.2(2) 3_455 3_455 ?
O15 Zn2 O2 89.9(2) . . ?
O15 Zn2 O2 90.1(2) 3_455 . ?
O14 Zn2 O2 90.2(2) . . ?
O14 Zn2 O2 89.8(2) 3_455 . ?
O2 Zn2 O2 180.0 3_455 . ?
V5 O1 V2 97.5(2) . . ?
V5 O1 V3 154.8(3) . . ?
V2 O1 V3 96.1(2) . . ?
V4 O2 Zn2 126.0(3) . . ?
V4 O3 Zn1 120.8(3) . . ?
V4 O3 V5 121.6(2) . . ?
Zn1 O3 V5 117.2(2) . . ?
V3 O4 V1 145.6(3) 2_454 . ?
V3 O4 V2 103.4(2) 2_454 . ?
V1 O4 V2 110.9(2) . . ?
V5 O6 V1 147.3(3) 3_565 . ?
V2 O7 V1 144.5(3) 2_444 . ?
V2 O7 V3 105.8(2) 2_444 . ?
V1 O7 V3 109.7(2) . . ?
V4 O8 V1 167.3(3) 3 . ?
V4 O9 V3 120.5(3) 3 3 ?
V4 O9 Zn1 120.0(2) 3 . ?
V3 O9 Zn1 119.5(2) 3 . ?
V3 O10 V2 103.0(2) 4_666 4_666 ?
V3 O10 Zn1 120.6(3) 4_666 . ?
V2 O10 Zn1 124.0(3) 4_666 . ?
V5 O12 V2 102.3(2) 3_565 3_565 ?
V5 O12 Zn1 122.3(2) 3_565 . ?
V2 O12 Zn1 119.0(3) 3_565 . ?
V3 O14 Zn2 145.2(3) . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O15 H15A O5 0.97(2) 2.29(2) 3.202(8) 156(4) 3_455
O15 H15A O11 0.97(2) 2.29(2) 2.831(8) 115(2) 1_545
O15 H15B O12 0.96(2) 2.02(2) 2.969(8) 170(8) 3
N16 HN1 O10 0.91(2) 2.17(4) 3.013(9) 153(6) 4_666
N16 HN1 O11 0.91(2) 2.54(5) 3.279(9) 138(6) 1_656
N16 HN2 O5 0.91(2) 2.06(3) 2.960(9) 170(7) 4_666
N16 HN3 O13 0.91(2) 1.92(4) 2.754(9) 153(7) 1_556
N16 HN4 O2 0.92(2) 2.27(4) 3.131(10) 156(6) 3_556
N16 HN4 O14 0.92(2) 2.32(7) 2.796(8) 112(5) 1_656
O13 H13A O14 0.96(2) 2.22(2) 3.122(7) 156(7) 2_454

_refine_diff_density_max         1.336
_refine_diff_density_min         -1.034
_refine_diff_density_rms         0.259

