# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.
# 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_shelxl
_database_code_depnum_ccdc_archive 'CCDC 2061511'
loop_
_audit_author_name
_audit_author_address
'Koji Nakabayashi'
;The University of Tokyo
Japan
;
_audit_update_record             
;
2021-02-06 deposited with the CCDC.	2021-07-02 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT420_shelxl              
;
PROBLEM: D-H Without Acceptor       O3       --H3B      .     Please Check
RESPONSE: The acceptor is not close to O3-H3B probably due to a weak interaction  between them.
;
# Added during the CSD deposition process: Saturday 06 February 2021 11:05 AM
# end Validation Reply Form

_audit_creation_date             2021-01-13
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2016/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         
'0.5(C48 H32 Mn6 N40 O8 W4), 2(H2 O), 2(C4 H4 N2)'
_chemical_formula_sum            'C32 H28 Mn3 N24 O6 W2'
_chemical_formula_weight         1377.30
_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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -0.8490 6.8722 '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'
N N 0.0061 0.0033 '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/n 1'
_space_group_name_Hall           '-P 2yn'
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                   7.2319(4)
_cell_length_b                   14.9477(8)
_cell_length_c                   22.4483(13)
_cell_angle_alpha                90
_cell_angle_beta                 90.920(6)
_cell_angle_gamma                90
_cell_volume                     2426.4(2)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    23250
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.464
_cell_measurement_theta_min      3.045
_shelx_estimated_absorpt_T_max   0.897
_shelx_estimated_absorpt_T_min   0.732
_exptl_absorpt_coefficient_mu    5.548
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.885
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             1318
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_exptl_transmission_factor_max   1.0000
_exptl_transmission_factor_min   0.6051
_diffrn_reflns_av_R_equivalents  0.0724
_diffrn_reflns_av_unetI/netI     0.0584
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            23250
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.464
_diffrn_reflns_theta_min         3.045
_diffrn_ambient_temperature      293.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       omega
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4861
_reflns_number_total             5547
_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       ?
_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    'SHELXS-97 (Sheldrick, 1990)'
_refine_diff_density_max         1.823
_refine_diff_density_min         -6.272
_refine_diff_density_rms         0.231
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.368
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     309
_refine_ls_number_reflns         5547
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0901
_refine_ls_R_factor_gt           0.0734
_refine_ls_restrained_S_all      1.368
_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)+24.5596P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0932
_refine_ls_wR_factor_ref         0.0964
_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:
 O3(H3A,H3B)
2.b Rotating group:
 O1(H1A,H1B), O2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
;


_atom_sites_solution_hydrogens   mixed
_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
W1 W 0.73781(4) 0.21377(2) 0.17819(2) 0.00849(8) Uani 1 1 d . . . . .
Mn1 Mn 0.24664(17) 0.47329(8) 0.23319(5) 0.0131(3) Uani 1 1 d . . . . .
Mn2 Mn 0.500000 0.500000 0.500000 0.0206(4) Uani 1 2 d S T P . .
O1 O 0.2298(9) 0.5350(5) 0.1476(3) 0.0318(17) Uani 1 1 d . . . . .
H1A H 0.319722 0.571030 0.143756 0.048 Uiso 1 1 d GR . . . .
H1B H 0.134132 0.568085 0.146018 0.048 Uiso 1 1 d GR . . . .
O2 O 0.2914(12) 0.5996(6) 0.4986(4) 0.056(2) Uani 1 1 d . . . . .
H2A H 0.191745 0.579758 0.516548 0.084 Uiso 1 1 d GR . . . .
H2B H 0.248384 0.610283 0.462070 0.084 Uiso 1 1 d GR . . . .
O3 O 0.6211(16) 0.8900(8) 0.1034(5) 0.080(3) Uani 1 1 d . . . . .
H3A H 0.651290 0.841797 0.121105 0.120 Uiso 1 1 d G . . . .
H3B H 0.681290 0.930557 0.121826 0.120 Uiso 1 1 d G . . . .
N1 N 0.4863(11) 0.3932(5) 0.2063(3) 0.0227(17) Uani 1 1 d . . . . .
N2 N 1.0664(11) 0.3616(5) 0.2039(4) 0.0271(19) Uani 1 1 d . . . . .
N3 N 0.8621(12) 0.0738(6) 0.0722(4) 0.032(2) Uani 1 1 d . . . . .
N4 N 1.0674(11) 0.0819(5) 0.2320(3) 0.0235(17) Uani 1 1 d . . . . .
N5 N 0.4971(11) 0.0470(6) 0.2337(4) 0.030(2) Uani 1 1 d . . . . .
N6 N 0.3516(13) 0.1873(6) 0.1004(4) 0.045(3) Uani 1 1 d . . . . .
N7 N 0.7870(13) 0.3300(6) 0.0540(4) 0.040(2) Uani 1 1 d . . . . .
N8 N 0.7457(17) 0.2464(7) 0.3242(4) 0.054(3) Uani 1 1 d . . . . .
N9 N 0.2777(12) 0.4015(5) 0.3250(4) 0.0240(17) Uani 1 1 d . . . . .
N10 N 0.3583(12) 0.4136(5) 0.4276(3) 0.0257(19) Uani 1 1 d . . . . .
N11 N 0.5633(12) 0.5637(7) 0.0884(4) 0.043(2) Uani 1 1 d . . . . .
N12 N 0.8914(12) 0.5581(6) 0.0879(4) 0.037(2) Uani 1 1 d . . . . .
C1 C 0.5727(12) 0.3315(6) 0.1958(4) 0.0180(19) Uani 1 1 d . . . . .
C2 C 0.9588(12) 0.3087(5) 0.1936(4) 0.0152(18) Uani 1 1 d . . . . .
C3 C 0.8178(13) 0.1198(6) 0.1098(4) 0.020(2) Uani 1 1 d . . . . .
C4 C 0.9570(13) 0.1300(5) 0.2141(4) 0.0176(19) Uani 1 1 d . . . . .
C5 C 0.5863(13) 0.1026(7) 0.2142(4) 0.023(2) Uani 1 1 d . . . . .
C6 C 0.4840(13) 0.1971(5) 0.1273(4) 0.022(2) Uani 1 1 d . . . . .
C7 C 0.7705(13) 0.2914(7) 0.0976(4) 0.025(2) Uani 1 1 d . . . . .
C8 C 0.7410(14) 0.2348(6) 0.2735(4) 0.025(2) Uani 1 1 d . . . . .
C9 C 0.3214(13) 0.4468(6) 0.3741(4) 0.025(2) Uani 1 1 d . . . . .
H9 H 0.326638 0.508689 0.370522 0.030 Uiso 1 1 calc R . . . .
C10 C 0.3449(16) 0.3256(7) 0.4321(5) 0.037(3) Uani 1 1 d . . . . .
H10 H 0.366763 0.299258 0.469049 0.045 Uiso 1 1 calc R . . . .
C11 C 0.3003(19) 0.2717(7) 0.3849(5) 0.051(3) Uani 1 1 d . . . . .
H11 H 0.290726 0.210000 0.389243 0.061 Uiso 1 1 calc R . . . .
C12 C 0.2704(16) 0.3121(6) 0.3312(5) 0.033(2) Uani 1 1 d . . . . .
H12 H 0.244198 0.276937 0.297952 0.040 Uiso 1 1 calc R . . . .
C13 C 0.7282(14) 0.5452(7) 0.1113(5) 0.034(3) Uani 1 1 d . . . . .
H13 H 0.728902 0.519547 0.149072 0.041 Uiso 1 1 calc R . . . .
C14 C 0.5653(18) 0.6009(10) 0.0342(6) 0.061(4) Uani 1 1 d . . . . .
H14 H 0.453424 0.615541 0.015698 0.073 Uiso 1 1 calc R . . . .
C15 C 0.725(2) 0.6179(11) 0.0054(6) 0.065(4) Uani 1 1 d . . . . .
H15 H 0.725073 0.643554 -0.032393 0.078 Uiso 1 1 calc R . . . .
C16 C 0.8863(17) 0.5958(9) 0.0342(6) 0.049(3) Uani 1 1 d . . . . .
H16 H 0.997564 0.607649 0.015566 0.059 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
W1 C1 2.166(9) . ?
W1 C2 2.161(8) . ?
W1 C3 2.167(9) . ?
W1 C4 2.165(9) . ?
W1 C5 2.154(10) . ?
W1 C6 2.161(9) . ?
W1 C7 2.165(10) . ?
W1 C8 2.162(9) . ?
Mn1 O1 2.133(6) . ?
Mn1 N1 2.199(8) . ?
Mn1 N2 2.211(8) 1_455 ?
Mn1 N4 2.241(8) 2_655 ?
Mn1 N5 2.217(8) 2 ?
Mn1 N9 2.331(8) . ?
Mn2 O2 2.119(8) . ?
Mn2 O2 2.119(8) 3_666 ?
Mn2 N3 2.212(8) 2_655 ?
Mn2 N3 2.212(8) 4_566 ?
Mn2 N10 2.304(8) . ?
Mn2 N10 2.304(8) 3_666 ?
O1 H1A 0.8502 . ?
O1 H1B 0.8505 . ?
O2 H2A 0.8831 . ?
O2 H2B 0.8861 . ?
O3 H3A 0.8501 . ?
O3 H3B 0.8496 . ?
N1 C1 1.141(11) . ?
N2 C2 1.131(11) . ?
N3 C3 1.137(11) . ?
N4 C4 1.142(11) . ?
N5 C5 1.144(12) . ?
N6 C6 1.133(12) . ?
N7 C7 1.143(12) . ?
N8 C8 1.152(12) . ?
N9 C9 1.328(12) . ?
N9 C12 1.344(11) . ?
N10 C9 1.321(12) . ?
N10 C10 1.324(12) . ?
N11 C13 1.320(13) . ?
N11 C14 1.337(15) . ?
N12 C13 1.314(13) . ?
N12 C16 1.330(14) . ?
C9 H9 0.9300 . ?
C10 H10 0.9300 . ?
C10 C11 1.365(15) . ?
C11 H11 0.9300 . ?
C11 C12 1.363(14) . ?
C12 H12 0.9300 . ?
C13 H13 0.9300 . ?
C14 H14 0.9300 . ?
C14 C15 1.360(18) . ?
C15 H15 0.9300 . ?
C15 C16 1.364(18) . ?
C16 H16 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
C1 W1 C3 144.1(3) . . ?
C2 W1 C1 81.1(3) . . ?
C2 W1 C3 109.5(3) . . ?
C2 W1 C4 77.6(3) . . ?
C2 W1 C6 141.2(3) . . ?
C2 W1 C7 72.0(3) . . ?
C2 W1 C8 75.5(3) . . ?
C4 W1 C1 143.5(3) . . ?
C4 W1 C3 71.8(3) . . ?
C5 W1 C1 105.8(3) . . ?
C5 W1 C2 145.7(3) . . ?
C5 W1 C3 84.8(4) . . ?
C5 W1 C4 77.8(3) . . ?
C5 W1 C6 71.1(3) . . ?
C5 W1 C7 142.1(3) . . ?
C5 W1 C8 74.8(4) . . ?
C6 W1 C1 74.0(3) . . ?
C6 W1 C3 77.6(3) . . ?
C6 W1 C4 137.8(3) . . ?
C6 W1 C7 73.9(3) . . ?
C6 W1 C8 122.4(4) . . ?
C7 W1 C1 77.6(3) . . ?
C7 W1 C3 73.8(3) . . ?
C7 W1 C4 122.1(3) . . ?
C8 W1 C1 72.4(3) . . ?
C8 W1 C3 142.8(3) . . ?
C8 W1 C4 73.7(3) . . ?
C8 W1 C7 138.5(3) . . ?
O1 Mn1 N1 91.3(3) . . ?
O1 Mn1 N2 92.0(3) . 1_455 ?
O1 Mn1 N4 91.5(3) . 2_655 ?
O1 Mn1 N5 93.0(3) . 2 ?
O1 Mn1 N9 177.1(3) . . ?
N1 Mn1 N2 88.3(3) . 1_455 ?
N1 Mn1 N4 91.1(3) . 2_655 ?
N1 Mn1 N5 175.6(3) . 2 ?
N1 Mn1 N9 85.8(3) . . ?
N2 Mn1 N4 176.5(3) 1_455 2_655 ?
N2 Mn1 N5 90.4(3) 1_455 2 ?
N2 Mn1 N9 87.9(3) 1_455 . ?
N4 Mn1 N9 88.7(3) 2_655 . ?
N5 Mn1 N4 89.9(3) 2 2_655 ?
N5 Mn1 N9 89.9(3) 2 . ?
O2 Mn2 O2 180.0(5) . 3_666 ?
O2 Mn2 N3 91.9(3) . 4_566 ?
O2 Mn2 N3 91.9(3) 3_666 2_655 ?
O2 Mn2 N3 88.1(3) 3_666 4_566 ?
O2 Mn2 N3 88.1(3) . 2_655 ?
O2 Mn2 N10 94.3(3) . . ?
O2 Mn2 N10 85.7(3) 3_666 . ?
O2 Mn2 N10 94.3(3) 3_666 3_666 ?
O2 Mn2 N10 85.7(3) . 3_666 ?
N3 Mn2 N3 180.0 4_566 2_655 ?
N3 Mn2 N10 92.1(3) 4_566 . ?
N3 Mn2 N10 87.9(3) 2_655 . ?
N3 Mn2 N10 87.9(3) 4_566 3_666 ?
N3 Mn2 N10 92.1(3) 2_655 3_666 ?
N10 Mn2 N10 180.0(4) 3_666 . ?
Mn1 O1 H1A 109.4 . . ?
Mn1 O1 H1B 108.9 . . ?
H1A O1 H1B 104.5 . . ?
Mn2 O2 H2A 110.1 . . ?
Mn2 O2 H2B 112.3 . . ?
H2A O2 H2B 101.9 . . ?
H3A O3 H3B 104.6 . . ?
C1 N1 Mn1 159.0(7) . . ?
C2 N2 Mn1 171.6(8) . 1_655 ?
C3 N3 Mn2 168.5(9) . 2_645 ?
C4 N4 Mn1 172.1(7) . 2_645 ?
C5 N5 Mn1 161.0(8) . 2_545 ?
C9 N9 Mn1 121.2(6) . . ?
C9 N9 C12 115.4(9) . . ?
C12 N9 Mn1 123.1(7) . . ?
C9 N10 Mn2 120.8(6) . . ?
C9 N10 C10 115.3(9) . . ?
C10 N10 Mn2 122.4(7) . . ?
C13 N11 C14 114.8(10) . . ?
C13 N12 C16 114.4(10) . . ?
N1 C1 W1 178.7(8) . . ?
N2 C2 W1 175.3(8) . . ?
N3 C3 W1 176.8(8) . . ?
N4 C4 W1 176.3(8) . . ?
N5 C5 W1 175.9(9) . . ?
N6 C6 W1 179.1(9) . . ?
N7 C7 W1 177.8(9) . . ?
N8 C8 W1 178.9(10) . . ?
N9 C9 H9 116.4 . . ?
N10 C9 N9 127.2(9) . . ?
N10 C9 H9 116.4 . . ?
N10 C10 H10 118.5 . . ?
N10 C10 C11 123.0(10) . . ?
C11 C10 H10 118.5 . . ?
C10 C11 H11 121.4 . . ?
C12 C11 C10 117.2(9) . . ?
C12 C11 H11 121.4 . . ?
N9 C12 C11 121.8(9) . . ?
N9 C12 H12 119.1 . . ?
C11 C12 H12 119.1 . . ?
N11 C13 H13 115.7 . . ?
N12 C13 N11 128.7(10) . . ?
N12 C13 H13 115.7 . . ?
N11 C14 H14 118.9 . . ?
N11 C14 C15 122.2(12) . . ?
C15 C14 H14 118.9 . . ?
C14 C15 H15 121.5 . . ?
C14 C15 C16 117.0(12) . . ?
C16 C15 H15 121.5 . . ?
N12 C16 C15 123.0(11) . . ?
N12 C16 H16 118.5 . . ?
C15 C16 H16 118.5 . . ?

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
Mn1 N9 C9 N10 -173.8(8) . . . . ?
Mn1 N9 C12 C11 175.9(9) . . . . ?
Mn2 N10 C9 N9 164.6(8) . . . . ?
Mn2 N10 C10 C11 -164.8(10) . . . . ?
N10 C10 C11 C12 0(2) . . . . ?
N11 C14 C15 C16 0(2) . . . . ?
C9 N9 C12 C11 2.0(17) . . . . ?
C9 N10 C10 C11 1.5(17) . . . . ?
C10 N10 C9 N9 -1.9(15) . . . . ?
C10 C11 C12 N9 -2(2) . . . . ?
C12 N9 C9 N10 0.2(15) . . . . ?
C13 N11 C14 C15 0(2) . . . . ?
C13 N12 C16 C15 -1.0(19) . . . . ?
C14 N11 C13 N12 -0.3(19) . . . . ?
C14 C15 C16 N12 1(2) . . . . ?
C16 N12 C13 N11 0.8(18) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
