# Electronic Supplementary Material (ESI) for Nanoscale.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# 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. 
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data_1_Mn6V12
_database_code_depnum_ccdc_archive 'CCDC 2324078'
loop_
_audit_author_name
_audit_author_address
'Jiangwei Zhang'
;Inner Mongolia University
China
;
_audit_update_record             
;
2024-01-08 deposited with the CCDC.	2024-04-30 downloaded from the CCDC.
;
_audit_creation_date             2023-10-01
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         '1(C24 H96 B18 Mn6 N24 O60 V12)'
_chemical_formula_sum            C24H96B18Mn6N24O60V12
_chemical_formula_weight         2858.94
_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'
B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 '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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3368 0.7283 '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      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3'
_space_group_name_Hall           '-R 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, 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'
'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'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -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'
'-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'

_cell_length_a                   21.0608(4)
_cell_length_b                   21.0608(4)
_cell_length_c                   21.1268(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     8115.5(5)
_cell_formula_units_Z            3.00006
_cell_measurement_reflns_used    3176
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.236
_cell_measurement_theta_min      2.228
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    1.752
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.755
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             4273
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0559
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            20518
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        25.236
_diffrn_reflns_theta_max         25.236
_diffrn_reflns_theta_min         2.228
_diffrn_ambient_temperature      292.93
_diffrn_detector_area_resol_mean 16.0971
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       'ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2532
_reflns_number_total             3176
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_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 2014/5 (Sheldrick, 2014)'
_refine_diff_density_max         1.776
_refine_diff_density_min         -1.289
_refine_diff_density_rms         0.160
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     217
_refine_ls_number_reflns         3176
_refine_ls_number_restraints     108
_refine_ls_R_factor_all          0.0826
_refine_ls_R_factor_gt           0.0640
_refine_ls_restrained_S_all      1.089
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0917P)²+185.9345P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1623
_refine_ls_wR_factor_ref         0.1841
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
2. Restrained distances
 C4-C3 = C2-C1
 1.45 with sigma of 0.002
 N4-C2 = N1-C1 = N2-C3 = N3-C4
 1.5 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C4 \\sim C3 \\sim C2 \\sim N1 \\sim N2 \\sim N3 \\sim N4: within 3.8A
with sigma of 0.01 and sigma for terminal atoms of 0.03
4.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), N3(H3A,H3B), N4(H4A,H4B), C1(H1C,H1D), C4(H4C,H4D),
 C3(H3C,H3D), C2(H2C,H2D)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_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
Mn1 Mn 0.16849(6) 0.28846(5) 0.69108(5) 0.0283(3) Uani 1 1 d . . . . .
V1 V 0.33619(5) 0.51227(5) 0.57828(4) 0.0172(3) Uani 1 1 d . . . . .
V2 V 0.43581(5) 0.66875(5) 0.53451(4) 0.0175(3) Uani 1 1 d . . . . .
O1 O 0.3361(2) 0.4769(2) 0.66599(18) 0.0172(8) Uani 1 1 d . . . . .
O2 O 0.4742(3) 0.6698(3) 0.4689(2) 0.0341(11) Uani 1 1 d . . . . .
O3 O 0.1152(2) 0.3831(2) 0.5860(2) 0.0239(9) Uani 1 1 d . . . . .
O4 O 0.2599(2) 0.4899(2) 0.74398(19) 0.0207(9) Uani 1 1 d . . . . .
O5 O 0.2005(2) 0.3964(2) 0.66574(18) 0.0196(9) Uani 1 1 d . . . . .
O6 O 0.0445(2) 0.4431(2) 0.59182(19) 0.0237(9) Uani 1 1 d . . . . .
O7 O 0.3371(3) 0.4516(2) 0.5316(2) 0.0282(10) Uani 1 1 d . . . . .
O8 O 0.2356(2) 0.4915(2) 0.59036(19) 0.0211(9) Uani 1 1 d . . . . .
O9 O 0.0040(3) 0.3334(3) 0.5317(2) 0.0367(12) Uani 1 1 d . . . . .
O10 O 0.3353(2) 0.5898(2) 0.52962(18) 0.0208(9) Uani 1 1 d . . . . .
N1 N 0.0944(4) 0.2886(4) 0.7575(3) 0.0534(17) Uani 1 1 d D U . . .
H1A H 0.081914 0.252968 0.785850 0.064 Uiso 1 1 calc R . . . .
H1B H 0.113853 0.331333 0.777727 0.064 Uiso 1 1 calc R . . . .
N2 N 0.1578(5) 0.1904(4) 0.7306(4) 0.0707(19) Uani 1 1 d D U . . .
H2A H 0.180463 0.200482 0.767855 0.085 Uiso 1 1 calc R . . . .
H2B H 0.110546 0.158376 0.737055 0.085 Uiso 1 1 calc R . . . .
N3 N 0.2330(6) 0.2717(5) 0.6247(4) 0.076(2) Uani 1 1 d D U . . .
H3A H 0.208821 0.255055 0.588358 0.092 Uiso 1 1 calc R . . . .
H3B H 0.274451 0.313409 0.617143 0.092 Uiso 1 1 calc R . . . .
N4 N 0.0728(4) 0.2350(4) 0.6334(4) 0.0610(17) Uani 1 1 d D U . . .
H4A H 0.076272 0.263914 0.601328 0.073 Uiso 1 1 calc R . . . .
H4B H 0.068347 0.193747 0.617595 0.073 Uiso 1 1 calc R . . . .
C1 C 0.0289(5) 0.2760(5) 0.7194(4) 0.067(2) Uani 1 1 d D U . . .
H1C H -0.012012 0.263188 0.747702 0.080 Uiso 1 1 calc R . . . .
H1D H 0.040019 0.321043 0.697856 0.080 Uiso 1 1 calc R . . . .
C4 C 0.2493(7) 0.2150(6) 0.6541(6) 0.097(3) Uani 1 1 d D U . . .
H4C H 0.262998 0.192633 0.620665 0.117 Uiso 1 1 calc R . . . .
H4D H 0.291055 0.240108 0.682250 0.117 Uiso 1 1 calc R . . . .
C3 C 0.1887(7) 0.1576(6) 0.6893(6) 0.095(3) Uani 1 1 d D U . . .
H3C H 0.205856 0.130530 0.714326 0.114 Uiso 1 1 calc R . . . .
H3D H 0.151526 0.123771 0.660253 0.114 Uiso 1 1 calc R . . . .
C2 C 0.0079(5) 0.2181(5) 0.6730(4) 0.074(3) Uani 1 1 d D U . . .
H2C H -0.031279 0.214837 0.646519 0.089 Uiso 1 1 calc R . . . .
H2D H -0.009685 0.171415 0.694195 0.089 Uiso 1 1 calc R . . . .
B1 B 0.2649(4) 0.4367(4) 0.7036(3) 0.0197(14) Uani 1 1 d . . . . .
B2 B 0.0550(4) 0.3884(4) 0.5698(3) 0.0225(14) Uani 1 1 d . . . . .
B3 B 0.1749(4) 0.4359(4) 0.6273(3) 0.0202(14) Uani 1 1 d . . . . .


_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
Mn1 O5 2.093(4) . ?
Mn1 O6 2.266(4) 15_556 ?
Mn1 N1 2.100(7) . ?
Mn1 N2 2.133(8) . ?
Mn1 N3 2.102(9) . ?
Mn1 N4 2.131(8) . ?
V1 V2 3.0262(14) 3_565 ?
V1 V2 3.0338(14) . ?
V1 O1 1.997(4) . ?
V1 O4 1.958(4) 15_556 ?
V1 O7 1.622(4) . ?
V1 O8 1.953(4) . ?
V1 O10 1.938(4) . ?
V2 O2 1.600(4) . ?
V2 O4 1.975(4) 15_556 ?
V2 O8 1.957(4) 2_665 ?
V2 O10 1.932(4) . ?
V2 O10 1.946(4) 2_665 ?
O1 B1 1.526(8) . ?
O1 B3 1.527(8) 15_556 ?
O3 B2 1.372(8) . ?
O3 B3 1.477(8) . ?
O4 B1 1.453(8) . ?
O5 B1 1.432(8) . ?
O5 B3 1.444(8) . ?
O6 B1 1.505(8) 14_456 ?
O6 B2 1.357(8) . ?
O8 B3 1.456(8) . ?
O9 B2 1.378(8) . ?
N1 H1A 0.8900 . ?
N1 H1B 0.8900 . ?
N1 C1 1.501(8) . ?
N2 H2A 0.8900 . ?
N2 H2B 0.8900 . ?
N2 C3 1.453(9) . ?
N3 H3A 0.8900 . ?
N3 H3B 0.8900 . ?
N3 C4 1.530(9) . ?
N4 H4A 0.8900 . ?
N4 H4B 0.8900 . ?
N4 C2 1.487(8) . ?
C1 H1C 0.9700 . ?
C1 H1D 0.9700 . ?
C1 C2 1.450(2) . ?
C4 H4C 0.9700 . ?
C4 H4D 0.9700 . ?
C4 C3 1.449(2) . ?
C3 H3C 0.9700 . ?
C3 H3D 0.9700 . ?
C2 H2C 0.9700 . ?
C2 H2D 0.9700 . ?

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 Mn1 O6 63.64(15) . 15_556 ?
O5 Mn1 N1 90.3(2) . . ?
O5 Mn1 N2 166.7(3) . . ?
O5 Mn1 N3 97.3(3) . . ?
O5 Mn1 N4 97.7(2) . . ?
N1 Mn1 O6 93.7(2) . 15_556 ?
N1 Mn1 N2 91.2(3) . . ?
N1 Mn1 N3 171.7(3) . . ?
N1 Mn1 N4 82.9(3) . . ?
N2 Mn1 O6 103.1(3) . 15_556 ?
N3 Mn1 O6 92.6(3) . 15_556 ?
N3 Mn1 N2 82.1(3) . . ?
N3 Mn1 N4 92.8(3) . . ?
N4 Mn1 O6 161.1(2) . 15_556 ?
N4 Mn1 N2 95.6(3) . . ?
V2 V1 V2 75.27(4) 3_565 . ?
O1 V1 V2 124.00(12) . . ?
O1 V1 V2 123.45(12) . 3_565 ?
O4 V1 V2 112.38(12) 15_556 3_565 ?
O4 V1 V2 39.73(12) 15_556 . ?
O4 V1 O1 90.75(17) 15_556 . ?
O7 V1 V2 113.34(17) . . ?
O7 V1 V2 113.11(17) . 3_565 ?
O7 V1 O1 105.6(2) . . ?
O7 V1 O4 109.0(2) . 15_556 ?
O7 V1 O8 110.0(2) . . ?
O7 V1 O10 110.5(2) . . ?
O8 V1 V2 39.33(12) . 3_565 ?
O8 V1 V2 111.52(13) . . ?
O8 V1 O1 89.77(17) . . ?
O8 V1 O4 139.32(18) . 15_556 ?
O10 V1 V2 38.92(12) . 3_565 ?
O10 V1 V2 38.31(12) . . ?
O10 V1 O1 143.89(17) . . ?
O10 V1 O4 77.92(17) . 15_556 ?
O10 V1 O8 78.02(17) . . ?
V1 V2 V1 139.49(5) 2_665 . ?
O2 V2 V1 110.46(17) . . ?
O2 V2 V1 110.04(17) . 2_665 ?
O2 V2 O4 108.1(2) . 15_556 ?
O2 V2 O8 109.0(2) . 2_665 ?
O2 V2 O10 107.1(2) . . ?
O2 V2 O10 106.9(2) . 2_665 ?
O4 V2 V1 39.31(12) 15_556 . ?
O4 V2 V1 123.12(12) 15_556 2_665 ?
O8 V2 V1 122.24(12) 2_665 . ?
O8 V2 V1 39.24(12) 2_665 2_665 ?
O8 V2 O4 88.92(17) 2_665 15_556 ?
O10 V2 V1 38.72(12) 2_665 2_665 ?
O10 V2 V1 126.17(13) 2_665 . ?
O10 V2 V1 38.44(12) . . ?
O10 V2 V1 126.47(13) . 2_665 ?
O10 V2 O4 144.88(17) 2_665 15_556 ?
O10 V2 O4 77.62(17) . 15_556 ?
O10 V2 O8 77.72(17) 2_665 2_665 ?
O10 V2 O8 143.76(17) . 2_665 ?
O10 V2 O10 94.2(2) . 2_665 ?
B1 O1 V1 120.6(3) . . ?
B1 O1 B3 114.6(4) . 15_556 ?
B3 O1 V1 122.1(3) 15_556 . ?
B2 O3 B3 124.1(5) . . ?
V1 O4 V2 100.96(18) 14_456 14_456 ?
B1 O4 V1 129.7(4) . 14_456 ?
B1 O4 V2 129.3(4) . 14_456 ?
B1 O5 Mn1 101.3(3) . . ?
B1 O5 B3 119.3(5) . . ?
B3 O5 Mn1 139.3(4) . . ?
B1 O6 Mn1 91.7(3) 14_456 14_456 ?
B2 O6 Mn1 137.4(4) . 14_456 ?
B2 O6 B1 120.4(5) . 14_456 ?
V1 O8 V2 101.43(19) . 3_565 ?
B3 O8 V1 132.0(4) . . ?
B3 O8 V2 126.5(4) . 3_565 ?
V1 O10 V2 102.36(19) . 3_565 ?
V2 O10 V1 103.25(19) . . ?
V2 O10 V2 145.1(2) . 3_565 ?
Mn1 N1 H1A 110.8 . . ?
Mn1 N1 H1B 110.8 . . ?
H1A N1 H1B 108.8 . . ?
C1 N1 Mn1 105.0(5) . . ?
C1 N1 H1A 110.8 . . ?
C1 N1 H1B 110.8 . . ?
Mn1 N2 H2A 109.3 . . ?
Mn1 N2 H2B 109.3 . . ?
H2A N2 H2B 107.9 . . ?
C3 N2 Mn1 111.7(7) . . ?
C3 N2 H2A 109.3 . . ?
C3 N2 H2B 109.3 . . ?
Mn1 N3 H3A 110.5 . . ?
Mn1 N3 H3B 110.5 . . ?
H3A N3 H3B 108.7 . . ?
C4 N3 Mn1 106.0(7) . . ?
C4 N3 H3A 110.5 . . ?
C4 N3 H3B 110.5 . . ?
Mn1 N4 H4A 110.0 . . ?
Mn1 N4 H4B 110.0 . . ?
H4A N4 H4B 108.4 . . ?
C2 N4 Mn1 108.6(6) . . ?
C2 N4 H4A 110.0 . . ?
C2 N4 H4B 110.0 . . ?
N1 C1 H1C 109.1 . . ?
N1 C1 H1D 109.1 . . ?
H1C C1 H1D 107.9 . . ?
C2 C1 N1 112.3(8) . . ?
C2 C1 H1C 109.1 . . ?
C2 C1 H1D 109.2 . . ?
N3 C4 H4C 108.7 . . ?
N3 C4 H4D 108.7 . . ?
H4C C4 H4D 107.6 . . ?
C3 C4 N3 114.3(10) . . ?
C3 C4 H4C 108.7 . . ?
C3 C4 H4D 108.7 . . ?
N2 C3 H3C 109.8 . . ?
N2 C3 H3D 109.8 . . ?
C4 C3 N2 109.2(10) . . ?
C4 C3 H3C 109.8 . . ?
C4 C3 H3D 109.8 . . ?
H3C C3 H3D 108.3 . . ?
N4 C2 H2C 109.9 . . ?
N4 C2 H2D 109.9 . . ?
C1 C2 N4 108.8(8) . . ?
C1 C2 H2C 109.9 . . ?
C1 C2 H2D 109.9 . . ?
H2C C2 H2D 108.3 . . ?
O4 B1 O1 107.9(5) . . ?
O4 B1 O6 111.9(5) . 15_556 ?
O5 B1 O1 114.5(5) . . ?
O5 B1 O4 111.8(5) . . ?
O5 B1 O6 103.3(5) . 15_556 ?
O6 B1 O1 107.4(5) 15_556 . ?
O3 B2 O9 116.1(6) . . ?
O6 B2 O3 122.1(5) . . ?
O6 B2 O9 121.7(6) . . ?
O3 B3 O1 107.2(5) . 14_456 ?
O5 B3 O1 112.1(5) . 14_456 ?
O5 B3 O3 108.7(5) . . ?
O5 B3 O8 109.5(5) . . ?
O8 B3 O1 108.1(5) . 14_456 ?
O8 B3 O3 111.3(5) . . ?
