# Supplementary Information (SI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# 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_a
_database_code_depnum_ccdc_archive 'CCDC 2482490'
loop_
_audit_author_name
_audit_author_address
'Wei-Hong Zhang'
;Shaanxi Normal University
China
;
_audit_update_record             
;
2025-08-25 deposited with the CCDC.	2025-10-06 downloaded from the CCDC.
;
_audit_creation_date             2025-07-12
_audit_creation_method           
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        nia-d-TZB
_chemical_formula_moiety         'C24 H12 Mn3 N12 O7, 2(C9 H6 N3)'
_chemical_formula_sum            'C42 H24 Mn3 N18 O7'
_chemical_formula_weight         1057.61
_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 0.0181 0.0091 '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'
Mn Mn -0.5299 2.8052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 '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      hexagonal
_space_group_IT_number           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'x-y, x, z+1/2'
'-y, x-y, z'
'-x, -y, z+1/2'
'-x+y, -x, z'
'y, -x+y, z+1/2'
'-y, -x, -z+1/2'
'x-y, -y, -z'
'x, x-y, -z+1/2'
'y, x, -z'
'-x+y, y, -z+1/2'
'-x, -x+y, -z'
'-x, -y, -z'
'-x+y, -x, -z-1/2'
'y, -x+y, -z'
'x, y, -z-1/2'
'x-y, x, -z'
'-y, x-y, -z-1/2'
'y, x, z-1/2'
'-x+y, y, z'
'-x, -x+y, z-1/2'
'-y, -x, z'
'x-y, -y, z-1/2'
'x, x-y, z'

_cell_length_a                   17.1218(11)
_cell_length_b                   17.1218(11)
_cell_length_c                   19.1004(14)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4849.2(7)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9892
_cell_measurement_temperature    243.15
_cell_measurement_theta_max      68.18
_cell_measurement_theta_min      5.51
_shelx_estimated_absorpt_T_max   0.685
_shelx_estimated_absorpt_T_min   0.548
_exptl_absorpt_coefficient_mu    3.416
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5664
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0615 before and 0.0339 after correction.
The Ratio of minimum to maximum transmission is 0.7521.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.724
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1066
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0169
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            15162
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.270
_diffrn_reflns_theta_min         5.510
_diffrn_ambient_temperature      243.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.970
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1630
_reflns_number_total             1652
_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       'SAINT V8.40B (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         1.278
_refine_diff_density_min         -0.512
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     139
_refine_ls_number_reflns         1652
_refine_ls_number_restraints     164
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0468
_refine_ls_restrained_S_all      1.105
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0627P)²+4.1603P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1194
_refine_ls_wR_factor_ref         0.1201
_refine_special_details          ?
_olex2_refinement_description    
;
1. Restrained distances
 C01U-C00M
 1.47 with sigma of 0.01
 C2-C01E
 1.47 with sigma of 0.01
 O2-C01E = C01E-O1
 1.23 with sigma of 0.02
 O2-O1
 2.13 with sigma of 0.04
2. Restrained planarity
 N1, C00M, N01H, C01U, N3, N4
 with sigma of 0.1
 C00M, C1, C01U, C2, C00U, C021, C3, C01E
 with sigma of 0.1
 O2, O1, C2, C01E
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Mn00 \\sim N1 \\sim N01H \\sim C00M \\sim N4 \\sim N3 \\sim C1 \\sim C01U \\sim
C00U \\sim C021 \\sim C2 \\sim C3 \\sim O2 \\sim O1 \\sim C01E: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(N3) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C01E) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C00M) \\sim Ueq, Uanis(N1)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C2) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O2) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C00U) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Others
 Fixed Sof: N1(0.25) N01H(0.25) C00M(0.25) N4(0.25) N3(0.25) C1(0.25) H1(0.25)
 C01U(0.25) C00U(0.25) H00U(0.25) C021(0.25) H021(0.25) C2(0.25) C3(0.25)
 H3(0.25) O2(0.25) O1(0.25) C01E(0.25)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C00U(H00U), C021(H021), C3(H3), C012(H012), C015(H015)
5.b Fitted pentagon refined as free rotating group:
 N1(N01H,C00M,N4,N3)
5.c Fitted hexagon refined as free rotating group:
 C1(C01U,C00U,C021,C2,C3)
;
_atom_sites_solution_hydrogens   geom
_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
Mn00 Mn 0.26299(2) 0.52597(3) 0.250000 0.0162(2) Uani 1 4 d S T P . .
N1 N 0.3703(6) 0.5395(7) 0.1803(3) 0.034(3) Uani 0.25 1 d G U P A -1
N01H N 0.3739(6) 0.4881(4) 0.1234(4) 0.0276(17) Uani 0.25 1 d G U P A -1
C00M C 0.4510(6) 0.5452(6) 0.0825(2) 0.0289(17) Uani 0.25 1 d DG U P A -1
N4 N 0.4949(4) 0.6318(5) 0.1141(4) 0.0151(15) Uani 0.25 1 d G U P A -1
N3 N 0.4451(6) 0.6283(6) 0.1746(4) 0.032(2) Uani 0.25 1 d G U P A -1
N009 N 0.18767(11) 0.3753(2) 0.250000 0.0417(9) Uani 1 4 d S T P A .
N2 N -0.04594(12) 0.04594(12) 0.250000 0.0661(15) Uani 1 4 d S T P . .
C00O C 0.04362(14) 0.0872(3) 0.250000 0.0629(17) Uani 1 4 d S T P . .
C00R C 0.09395(13) 0.1879(3) 0.250000 0.0584(16) Uani 1 4 d S T P . .
C1 C 0.5752(5) 0.5666(5) 0.0041(3) 0.0286(19) Uani 0.25 1 d G U P A -1
H1 H 0.616728 0.617756 0.029441 0.034 Uiso 0.25 1 calc R U P A -1
C01U C 0.4853(6) 0.5191(5) 0.0248(2) 0.0391(13) Uani 0.25 1 d DG U P A -1
C00U C 0.4239(5) 0.4435(5) -0.0126(3) 0.035(2) Uani 0.25 1 d G U P A -1
H00U H 0.363099 0.411372 0.001386 0.042 Uiso 0.25 1 calc R U P A -1
C021 C 0.4522(5) 0.4153(5) -0.0707(3) 0.039(2) Uani 0.25 1 d G U P A -1
H021 H 0.410641 0.364195 -0.095947 0.047 Uiso 0.25 1 calc R U P A -1
C2 C 0.5420(6) 0.4628(6) -0.0913(3) 0.0307(18) Uani 0.25 1 d DG U P A -1
C3 C 0.6035(5) 0.5385(6) -0.0539(3) 0.028(2) Uani 0.25 1 d G U P A -1
H3 H 0.664270 0.570577 -0.067893 0.033 Uiso 0.25 1 calc R U P A -1
C012 C 0.1860(2) 0.2357(2) 0.250000 0.0839(18) Uani 1 2 d S T P A .
H012 H 0.219136 0.205490 0.250000 0.101 Uiso 1 2 calc R U P . .
C015 C 0.2300(2) 0.3286(2) 0.250000 0.0765(15) Uani 1 2 d S T P . .
H015 H 0.293373 0.360387 0.250000 0.092 Uiso 1 2 calc R U P A .
O2 O 0.6418(5) 0.4610(6) -0.1629(4) 0.0163(16) Uani 0.25 1 d D U P A -1
O1 O 0.5107(4) 0.3443(4) -0.1731(3) 0.0182(14) Uani 0.25 1 d D U P A -1
C01E C 0.5660(6) 0.4192(7) -0.1486(3) 0.0274(14) Uani 0.25 1 d D U P A -1
O3 O 0.333333 0.666667 0.250000 0.0101(7) Uiso 1 12 d S . P A .


_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
Mn00 N1 2.185(5) . ?
Mn00 N009 2.234(3) . ?
Mn00 O3 2.0862(5) . ?
N1 N01H 1.4200 . ?
N1 N3 1.4200 . ?
N01H C00M 1.4200 . ?
C00M N4 1.4200 . ?
C00M C01U 1.421(4) . ?
N4 N3 1.4200 . ?
N009 C015 1.321(4) 20 ?
N009 C015 1.320(4) . ?
N2 C00O 1.329(3) . ?
N2 C00O 1.329(3) 3 ?
C00O C00R 1.492(6) . ?
C00R C012 1.365(4) 20 ?
C00R C012 1.365(4) . ?
C1 H1 0.9400 . ?
C1 C01U 1.3900 . ?
C1 C3 1.3900 . ?
C01U C00U 1.3900 . ?
C00U H00U 0.9400 . ?
C00U C021 1.3900 . ?
C021 H021 0.9400 . ?
C021 C2 1.3900 . ?
C2 C3 1.3900 . ?
C2 C01E 1.493(6) . ?
C3 H3 0.9400 . ?
C012 H012 0.9400 . ?
C012 C015 1.378(4) . ?
C015 H015 0.9400 . ?
O2 C01E 1.159(11) . ?
O1 C01E 1.243(11) . ?

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
N1 Mn00 N009 95.3(3) . . ?
O3 Mn00 N1 84.7(3) . . ?
O3 Mn00 N009 180.00(3) . . ?
N01H N1 Mn00 134.1(6) . . ?
N3 N1 Mn00 114.9(6) . . ?
N3 N1 N01H 108.0 . . ?
C00M N01H N1 108.0 . . ?
N01H C00M N4 108.0 . . ?
N01H C00M C01U 126.8(8) . . ?
N4 C00M C01U 124.8(8) . . ?
C00M N4 N3 108.0 . . ?
N1 N3 N4 108.0 . . ?
C015 N009 Mn00 121.64(18) 20 . ?
C015 N009 Mn00 121.64(18) . . ?
C015 N009 C015 116.7(4) . 20 ?
C00O N2 C00O 114.9(4) 3 . ?
N2 C00O N2 125.1(4) . 14_556 ?
N2 C00O C00R 117.4(2) 14_556 . ?
N2 C00O C00R 117.4(2) . . ?
C012 C00R C00O 121.3(2) 20 . ?
C012 C00R C00O 121.3(2) . . ?
C012 C00R C012 117.4(4) 20 . ?
C01U C1 H1 120.0 . . ?
C01U C1 C3 120.0 . . ?
C3 C1 H1 120.0 . . ?
C1 C01U C00M 123.2(7) . . ?
C1 C01U C00U 120.0 . . ?
C00U C01U C00M 116.8(7) . . ?
C01U C00U H00U 120.0 . . ?
C021 C00U C01U 120.0 . . ?
C021 C00U H00U 120.0 . . ?
C00U C021 H021 120.0 . . ?
C00U C021 C2 120.0 . . ?
C2 C021 H021 120.0 . . ?
C021 C2 C01E 114.5(7) . . ?
C3 C2 C021 120.0 . . ?
C3 C2 C01E 125.0(6) . . ?
C1 C3 H3 120.0 . . ?
C2 C3 C1 120.0 . . ?
C2 C3 H3 120.0 . . ?
C00R C012 H012 120.2 . . ?
C00R C012 C015 119.5(3) . . ?
C015 C012 H012 120.2 . . ?
N009 C015 C012 123.4(3) . . ?
N009 C015 H015 118.3 . . ?
C012 C015 H015 118.3 . . ?
C01E O2 Mn00 139.9(7) . 4_664 ?
O2 C01E C2 111.5(9) . . ?
O2 C01E O1 126.1(6) . . ?
O1 C01E C2 122.3(8) . . ?
Mn00 O3 Mn00 120.0 14_566 3_665 ?
Mn00 O3 Mn00 120.0 3_665 . ?
Mn00 O3 Mn00 120.0 14_566 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Mn00 N1 N01H C00M 158.6(6) . . . . ?
Mn00 N1 N3 N4 -163.2(5) . . . . ?
Mn00 N009 C015 C012 180.0 . . . . ?
Mn00 O2 C01E C2 -163.2(8) 4_664 . . . ?
Mn00 O2 C01E O1 21.4(14) 4_664 . . . ?
N1 N01H C00M N4 0.0 . . . . ?
N1 N01H C00M C01U 173.2(7) . . . . ?
N01H N1 N3 N4 0.0 . . . . ?
N01H C00M N4 N3 0.0 . . . . ?
N01H C00M C01U C1 -154.8(5) . . . . ?
N01H C00M C01U C00U 26.7(7) . . . . ?
C00M N4 N3 N1 0.0 . . . . ?
C00M C01U C00U C021 178.5(5) . . . . ?
N4 C00M C01U C1 17.2(7) . . . . ?
N4 C00M C01U C00U -161.2(5) . . . . ?
N3 N1 N01H C00M 0.0 . . . . ?
N2 C00O C00R C012 0.0 14_556 . . . ?
N2 C00O C00R C012 0.0 . . . 20 ?
N2 C00O C00R C012 180.0 . . . . ?
N2 C00O C00R C012 180.0 14_556 . . 20 ?
C00O N2 C00O N2 0.0 3 . . 14_556 ?
C00O N2 C00O C00R 180.0 3 . . . ?
C00O C00R C012 C015 180.0 . . . . ?
C00R C012 C015 N009 0.0 . . . . ?
C1 C01U C00U C021 0.0 . . . . ?
C01U C00M N4 N3 -173.3(6) . . . . ?
C01U C1 C3 C2 0.0 . . . . ?
C01U C00U C021 C2 0.0 . . . . ?
C00U C021 C2 C3 0.0 . . . . ?
C00U C021 C2 C01E 172.6(5) . . . . ?
C021 C2 C3 C1 0.0 . . . . ?
C021 C2 C01E O2 -178.9(6) . . . . ?
C021 C2 C01E O1 -3.4(8) . . . . ?
C3 C1 C01U C00M -178.4(5) . . . . ?
C3 C1 C01U C00U 0.0 . . . . ?
C3 C2 C01E O2 -6.7(8) . . . . ?
C3 C2 C01E O1 168.9(5) . . . . ?
C012 C00R C012 C015 0.0 20 . . . ?
C015 N009 C015 C012 0.0 20 . . . ?
C01E C2 C3 C1 -171.8(6) . . . . ?

_smtbx_masks_special_details     ?
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 -0.624 -0.273 -0.369 2966.9 324.9 ?

_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# 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_a_CCDC1
_database_code_depnum_ccdc_archive 'CCDC 2482491'
loop_
_audit_author_name
_audit_author_address
'Wei-Hong Zhang'
;Shaanxi Normal University
China
;
_audit_update_record             
;
2025-08-25 deposited with the CCDC.	2025-10-06 downloaded from the CCDC.
;
_audit_creation_date             2025-07-12
_audit_creation_method           
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        nia-d-FTZB
_chemical_formula_moiety         'C42 H21 F3 Mn3 N18 O7'
_chemical_formula_sum            'C42 H21 F3 Mn3 N18 O7'
_chemical_formula_weight         1111.57
_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 0.0181 0.0091 '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'
F F 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn -0.5299 2.8052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 '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      hexagonal
_space_group_IT_number           194
_space_group_name_H-M_alt        'P 63/m m c'
_space_group_name_Hall           '-P 6c 2c'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, z+1/2'
'y, -x+y, z+1/2'
'x-y, x, z+1/2'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -z'
'-y, -x, -z+1/2'
'-x+y, y, -z+1/2'
'x, x-y, -z+1/2'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'x, y, -z-1/2'
'-y, x-y, -z-1/2'
'-x+y, -x, -z-1/2'
'-y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'y, x, z-1/2'
'x-y, -y, z-1/2'
'-x, -x+y, z-1/2'

_cell_length_a                   17.0909(9)
_cell_length_b                   17.0909(9)
_cell_length_c                   19.1443(15)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     4842.8(6)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    9901
_cell_measurement_temperature    243.00
_cell_measurement_theta_max      68.08
_cell_measurement_theta_min      5.50
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    3.482
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.6759
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0443 before and 0.0373 after correction.
The Ratio of minimum to maximum transmission is 0.8976.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.762
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1114
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0292
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            14993
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.088
_diffrn_reflns_theta_min         5.504
_diffrn_ambient_temperature      243.00
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_oxdiff_ac3_digest_hkl    013836d76bed2d79ea4955ded1a69cd711df38
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_diffrn_source_current           50.0
_diffrn_source_power             2.5
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1624
_reflns_number_total             1673
_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       'SAINT V8.40B (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         0.673
_refine_diff_density_min         -0.394
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     149
_refine_ls_number_reflns         1673
_refine_ls_number_restraints     151
_refine_ls_R_factor_all          0.0543
_refine_ls_R_factor_gt           0.0529
_refine_ls_restrained_S_all      1.180
_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)+(0.0884P)²+4.3897P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1441
_refine_ls_wR_factor_ref         0.1463
_refine_special_details          ?
_olex2_refinement_description    
;
1. Restrained distances
 C1-C00E
 1.47 with sigma of 0.01
 C00C-C008
 1.36 with sigma of 0.01
 O1-C00C = C00C-O004
 1.23 with sigma of 0.02
 F11-C3
 1.43 with sigma of 0.01
 O1-O004
 2.13 with sigma of 0.04
 C1-C00D \\sim C2-C1
 with sigma of 0.02
 Mn01_$3-O1 \\sim Mn01_$4-O004
 with sigma of 0.02
 F11-C00D \\sim F11-C008
 with sigma of 0.02
2. Restrained planarity
 N1, C1, N2, C00E, N004, N00B
 with sigma of 0.1
 C1, C00D, C00E, C008, C2, C3, C4, F11, C00C
 with sigma of 0.1
 C00C, O1, O004, C008
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Mn01 \\sim N1 \\sim N2 \\sim C1 \\sim N00B \\sim N004 \\sim C00D \\sim C3 \\sim
C008 \\sim C4 \\sim C2 \\sim C00E \\sim O004 \\sim O1 \\sim C00C \\sim F11:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(O004) \\sim Ueq, Uanis(C00C) \\sim Ueq, Uanis(N00B) \\sim Ueq,
Uanis(N004) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1) \\sim Ueq, Uanis(O004) \\sim Ueq, Uanis(N00B) \\sim Ueq, Uanis(N004)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N004) \\sim Ueq, Uanis(N00B) \\sim Ueq, Uanis(O004) \\sim Ueq, Uanis(O1)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(N1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Others
 Fixed Sof: N1(0.25) N2(0.25) C1(0.25) N00B(0.25) N004(0.25) C00D(0.25)
 H00D(0.25) C3(0.25) C008(0.125) C4(0.25) H4(0.25) C2(0.25) H2(0.25) C00E(0.25)
 O004(0.25) O1(0.25) C00C(0.25) F11(0.25)
5.a Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00A), C00D(H00D), C4(H4), C2(H2)
5.b Fitted pentagon refined as free rotating group:
 N1(N2,C1,N00B,N004)
5.c Fitted hexagon refined as free rotating group:
 C00D(C3,C008,C4,C2,C00E)
;
_atom_sites_solution_hydrogens   geom
_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
Mn01 Mn 0.26300(2) 0.73700(2) 0.750000 0.0200(3) Uani 1 4 d S T P . .
O002 O 0.333333 0.666667 0.750000 0.0121(8) Uani 1 12 d S T P A .
N003 N 0.18792(12) 0.81208(12) 0.750000 0.0461(11) Uani 1 4 d S T P A .
N1 N 0.1674(5) 0.6293(6) 0.6812(3) 0.035(3) Uani 0.25 1 d G U P A -1
N2 N 0.1137(6) 0.6284(6) 0.6243(4) 0.035(2) Uani 0.25 1 d G U P A -1
C1 C 0.0935(5) 0.5525(7) 0.5818(3) 0.043(3) Uani 0.25 1 d DG U P A -1
N00B N 0.1347(5) 0.5064(5) 0.6125(4) 0.0201(17) Uani 0.25 1 d G U P A -1
N004 N 0.1803(5) 0.5538(6) 0.6739(4) 0.025(2) Uani 0.25 1 d G U P A -1
N005 N -0.04603(13) 0.9079(3) 0.750000 0.0652(17) Uani 1 4 d S T P . .
C006 C 0.09412(16) 0.90588(16) 0.750000 0.0601(18) Uani 1 4 d S T P . .
C007 C 0.04385(16) 0.95615(16) 0.750000 0.0621(19) Uani 1 4 d S T P . .
C009 C 0.0990(3) 0.7697(3) 0.750000 0.0859(19) Uani 1 2 d S T P . .
H009 H 0.067318 0.706157 0.750000 0.103 Uiso 1 2 calc R U P A .
C00A C 0.0497(3) 0.8142(3) 0.750000 0.092(2) Uani 1 2 d S T P A .
H00A H -0.013782 0.781125 0.750000 0.110 Uiso 1 2 calc R U P . .
C00D C 0.0247(5) 0.4481(7) 0.4851(4) 0.064(4) Uani 0.25 1 d DG U P A -1
H00D H 0.057669 0.419879 0.497870 0.077 Uiso 0.25 1 calc R U P A -1
C3 C -0.0327(6) 0.4171(7) 0.4277(5) 0.072(3) Uani 0.25 1 d DG U P A -1
C008 C -0.0815(6) 0.4589(8) 0.4088(4) 0.045(3) Uani 0.25 1 d DG U P A -1
C4 C -0.0730(6) 0.5317(7) 0.4474(5) 0.060(3) Uani 0.25 1 d G U P A -1
H4 H -0.105976 0.559978 0.434683 0.072 Uiso 0.25 1 calc R U P A -1
C2 C -0.0156(5) 0.5627(7) 0.5049(4) 0.062(4) Uani 0.25 1 d DG U P A -1
H2 H -0.009776 0.611928 0.530958 0.075 Uiso 0.25 1 calc R U P A -1
C00E C 0.0332(4) 0.5209(7) 0.5237(3) 0.052(2) Uani 0.25 1 d DG U P A -1
O004 O -0.1849(5) 0.4604(6) 0.3390(4) 0.0238(18) Uani 0.25 1 d D U P A -1
O1 O -0.1651(4) 0.3461(4) 0.3268(4) 0.0197(15) Uani 0.25 1 d D U P A -1
C00C C -0.1463(5) 0.4197(9) 0.3524(3) 0.0315(18) Uani 0.25 1 d D U P A -1
F11 F -0.0542(11) 0.3304(8) 0.4036(7) 0.175(5) Uani 0.25 1 d D U P A -1


_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
Mn01 O002 2.0820(6) . ?
Mn01 N003 2.223(4) . ?
Mn01 N1 2.188(5) . ?
N003 C009 1.317(4) 19_665 ?
N003 C009 1.317(4) . ?
N1 N2 1.4200 . ?
N1 N004 1.4200 . ?
N2 C1 1.4200 . ?
C1 N00B 1.4200 . ?
C1 C00E 1.426(4) . ?
N00B N004 1.4200 . ?
N005 C007 1.331(3) . ?
N005 C007 1.331(3) 3_465 ?
C006 C007 1.488(6) . ?
C006 C00A 1.358(5) 19_665 ?
C006 C00A 1.358(5) . ?
C009 H009 0.9400 . ?
C009 C00A 1.389(5) . ?
C00A H00A 0.9400 . ?
C00D H00D 0.9400 . ?
C00D C3 1.3900 . ?
C00D C00E 1.3900 . ?
C3 C008 1.3900 . ?
C3 F11 1.415(9) . ?
C008 C4 1.3900 . ?
C008 C00C 1.449(6) . ?
C4 H4 0.9400 . ?
C4 C2 1.3900 . ?
C2 H2 0.9400 . ?
C2 C00E 1.3900 . ?
O004 C00C 1.202(14) . ?
O1 C00C 1.234(14) . ?

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
O002 Mn01 N003 180.0 . . ?
O002 Mn01 N1 85.3(3) . . ?
N1 Mn01 N003 94.7(3) . . ?
Mn01 O002 Mn01 120.0 . 3_565 ?
Mn01 O002 Mn01 120.0 . 2_665 ?
Mn01 O002 Mn01 120.0 3_565 2_665 ?
C009 N003 Mn01 121.5(2) . . ?
C009 N003 Mn01 121.5(2) 19_665 . ?
C009 N003 C009 117.0(4) . 19_665 ?
N2 N1 Mn01 132.7(6) . . ?
N2 N1 N004 108.0 . . ?
N004 N1 Mn01 115.6(6) . . ?
N1 N2 C1 108.0 . . ?
N2 C1 N00B 108.0 . . ?
N2 C1 C00E 126.3(7) . . ?
N00B C1 C00E 125.3(7) . . ?
N004 N00B C1 108.0 . . ?
N00B N004 N1 108.0 . . ?
C007 N005 C007 115.2(5) 3_465 . ?
C00A C006 C007 121.0(2) . . ?
C00A C006 C007 121.0(2) 19_665 . ?
C00A C006 C00A 117.9(5) . 19_665 ?
N005 C007 N005 124.8(5) 2_675 . ?
N005 C007 C006 117.6(2) 2_675 . ?
N005 C007 C006 117.6(2) . . ?
N003 C009 H009 118.4 . . ?
N003 C009 C00A 123.2(3) . . ?
C00A C009 H009 118.4 . . ?
C006 C00A C009 119.4(3) . . ?
C006 C00A H00A 120.3 . . ?
C009 C00A H00A 120.3 . . ?
C3 C00D H00D 120.0 . . ?
C3 C00D C00E 120.0 . . ?
C00E C00D H00D 120.0 . . ?
C00D C3 C008 120.0 . . ?
C00D C3 F11 114.9(6) . . ?
C008 C3 F11 123.1(6) . . ?
C3 C008 C00C 118.1(8) . . ?
C4 C008 C3 120.0 . . ?
C4 C008 C00C 121.7(8) . . ?
C008 C4 H4 120.0 . . ?
C008 C4 C2 120.0 . . ?
C2 C4 H4 120.0 . . ?
C4 C2 H2 120.0 . . ?
C4 C2 C00E 120.0 . . ?
C00E C2 H2 120.0 . . ?
C00D C00E C1 119.1(6) . . ?
C2 C00E C1 120.9(6) . . ?
C2 C00E C00D 120.0 . . ?
C00C O004 Mn01 138.5(7) . 9_556 ?
C00C O1 Mn01 131.8(6) . 13_566 ?
O004 C00C C008 113.9(11) . . ?
O004 C00C O1 124.5(7) . . ?
O1 C00C C008 121.2(11) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Mn01 N003 C009 C00A 180.000(0) . . . . ?
Mn01 N1 N2 C1 156.7(7) . . . . ?
Mn01 N1 N004 N00B -161.2(5) . . . . ?
Mn01 O004 C00C C008 160.1(8) 9_556 . . . ?
Mn01 O004 C00C O1 -27.2(17) 9_556 . . . ?
Mn01 O1 C00C C008 174.5(7) 13_566 . . . ?
Mn01 O1 C00C O004 2.3(14) 13_566 . . . ?
N003 C009 C00A C006 0.000(0) . . . . ?
N1 N2 C1 N00B 0.0 . . . . ?
N1 N2 C1 C00E 172.7(7) . . . . ?
N2 N1 N004 N00B 0.0 . . . . ?
N2 C1 N00B N004 0.0 . . . . ?
N2 C1 C00E C00D 176.5(5) . . . . ?
N2 C1 C00E C2 -2.6(8) . . . . ?
C1 N00B N004 N1 0.0 . . . . ?
N00B C1 C00E C00D -12.0(8) . . . . ?
N00B C1 C00E C2 168.9(6) . . . . ?
N004 N1 N2 C1 0.0 . . . . ?
C007 N005 C007 N005 0.0 3_465 . . 2_675 ?
C007 N005 C007 C006 180.0 3_465 . . . ?
C007 C006 C00A C009 180.000(0) . . . . ?
C009 N003 C009 C00A 0.000(0) 19_665 . . . ?
C00A C006 C007 N005 0.0 . . . . ?
C00A C006 C007 N005 0.0 19_665 . . 2_675 ?
C00A C006 C007 N005 180.0 . . . 2_675 ?
C00A C006 C007 N005 180.0 19_665 . . . ?
C00A C006 C00A C009 0.000(0) 19_665 . . . ?
C00D C3 C008 C4 0.0 . . . . ?
C00D C3 C008 C00C -174.8(8) . . . . ?
C3 C00D C00E C1 -179.1(6) . . . . ?
C3 C00D C00E C2 0.0 . . . . ?
C3 C008 C4 C2 0.0 . . . . ?
C3 C008 C00C O004 -179.3(7) . . . . ?
C3 C008 C00C O1 7.7(11) . . . . ?
C008 C4 C2 C00E 0.0 . . . . ?
C4 C008 C00C O004 6.0(12) . . . . ?
C4 C008 C00C O1 -166.9(7) . . . . ?
C4 C2 C00E C1 179.1(6) . . . . ?
C4 C2 C00E C00D 0.0 . . . . ?
C00E C1 N00B N004 -172.8(7) . . . . ?
C00E C00D C3 C008 0.0 . . . . ?
C00E C00D C3 F11 -164.4(11) . . . . ?
C00C C008 C4 C2 174.6(9) . . . . ?
F11 C3 C008 C4 163.1(12) . . . . ?
F11 C3 C008 C00C -11.7(12) . . . . ?

_smtbx_masks_special_details     ?
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 -0.423 -0.296 -0.642 2763.4 273.0 ?

_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_submission_special_instructions 'No special instructions were received'
