# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# 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_20180810e1_1
_database_code_depnum_ccdc_archive 'CCDC 1865015'
_audit_update_record             
;
2018-08-31 deposited with the CCDC.
2019-01-11 downloaded from the CCDC.
;
_audit_creation_date             2018-08-30
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelxl_version_number           2013-2
_chemical_name_common            ?
_chemical_name_systematic        Mn-CCs
_chemical_formula_moiety         '0.17(C216 H132 Mn54 O180 P24)'
_chemical_formula_sum            'C36 H21 Mn9 O29 P4'
_chemical_formula_weight         1535.87
_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'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.2955 0.4335 '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      cubic
_space_group_IT_number           223
_space_group_name_H-M_alt        'P m -3 n'
_space_group_name_Hall           '-P 4n 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y+1/2, x+1/2, -z+1/2'
'-y+1/2, -x+1/2, -z+1/2'
'y+1/2, -x+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'x+1/2, z+1/2, -y+1/2'
'-x+1/2, z+1/2, y+1/2'
'-x+1/2, -z+1/2, -y+1/2'
'x+1/2, -z+1/2, y+1/2'
'z+1/2, y+1/2, -x+1/2'
'z+1/2, -y+1/2, x+1/2'
'-z+1/2, y+1/2, x+1/2'
'-z+1/2, -y+1/2, -x+1/2'
'-x, -y, -z'
'x, y, -z'
'x, -y, z'
'-x, y, z'
'-z, -x, -y'
'-z, x, y'
'z, x, -y'
'z, -x, y'
'-y, -z, -x'
'y, -z, x'
'-y, z, x'
'y, z, -x'
'-y-1/2, -x-1/2, z-1/2'
'y-1/2, x-1/2, z-1/2'
'-y-1/2, x-1/2, -z-1/2'
'y-1/2, -x-1/2, -z-1/2'
'-x-1/2, -z-1/2, y-1/2'
'x-1/2, -z-1/2, -y-1/2'
'x-1/2, z-1/2, y-1/2'
'-x-1/2, z-1/2, -y-1/2'
'-z-1/2, -y-1/2, x-1/2'
'-z-1/2, y-1/2, -x-1/2'
'z-1/2, -y-1/2, -x-1/2'
'z-1/2, y-1/2, x-1/2'

_cell_length_a                   22.2297(2)
_cell_length_b                   22.2297(2)
_cell_length_c                   22.2297(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     10985.0(3)
_cell_formula_units_Z            6
_cell_measurement_reflns_used    2428
_cell_measurement_temperature    298
_cell_measurement_theta_max      68.9350
_cell_measurement_theta_min      4.4590
_shelx_estimated_absorpt_T_max   0.172
_shelx_estimated_absorpt_T_min   0.172
_exptl_absorpt_coefficient_mu    13.600
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67423
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             4524
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0505
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            10898
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.431
_diffrn_reflns_theta_min         3.977
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -23.00   8.00   0.50    1.00    --    0.00  57.00 -90.00   62
  2  ω     64.00  89.00   0.50    1.00    --    0.00  57.00 -90.00   50
  3  ω     41.00  69.00   0.50   15.00    --   97.60 -41.00 136.00   56
  4  ω     91.00 181.00   0.50   15.00    --   97.60  30.00  90.00  180
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0540539000
_diffrn_orient_matrix_UB_12      -0.0312923000
_diffrn_orient_matrix_UB_13      0.0303545000
_diffrn_orient_matrix_UB_21      0.0320145000
_diffrn_orient_matrix_UB_22      0.0044060000
_diffrn_orient_matrix_UB_23      0.0611785000
_diffrn_orient_matrix_UB_31      -0.0294624000
_diffrn_orient_matrix_UB_32      0.0617137000
_diffrn_orient_matrix_UB_33      0.0110576000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1244
_reflns_number_total             1798
_reflns_odcompleteness_completeness 99.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (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         1.956
_refine_diff_density_min         -1.228
_refine_diff_density_rms         0.187
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     106
_refine_ls_number_reflns         1798
_refine_ls_number_restraints     18
_refine_ls_R_factor_all          0.1350
_refine_ls_R_factor_gt           0.1159
_refine_ls_restrained_S_all      1.104
_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)+(0.3000P)²]
 where P=(Fo²+2Fc²)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3626
_refine_ls_wR_factor_ref         0.3822
_refine_special_details          SQUEEZE
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O2) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: H6A(0.5) H6B(0.5) O6(0.25) H6(0.25)
4.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4)
4.c Tetrahedral OH refined with riding coordinates:
 O6(H6)
;
_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
Mn1 Mn 0.64570(7) 0.2500 0.14570(7) 0.0567(8) Uani 1 2 d S T P . .
Mn3 Mn 0.5000 0.2500 0.0000 0.0614(11) Uani 1 8 d S T P . .
Mn2 Mn 0.5000 0.33108(11) 0.18991(19) 0.0951(12) Uani 1 2 d S T P . .
P1 P 0.5000 0.21340(15) 0.14072(14) 0.0608(10) Uani 1 2 d S T P . .
O4 O 0.5534(3) 0.2512(3) 0.1618(3) 0.0637(17) Uani 1 1 d . . . . .
O3 O 0.5000 0.1979(5) 0.0763(4) 0.086(3) Uani 1 2 d S T P . .
O2 O 0.6586(4) 0.1548(5) 0.3479(4) 0.093(3) Uani 1 1 d . U . . .
C5 C 0.5000 0.1550(5) 0.2505(5) 0.047(3) Uani 1 2 d S T P . .
C6 C 0.5000 0.1445(5) 0.1839(5) 0.046(2) Uani 1 2 d S T P . .
H6A H 0.4648 0.1211 0.1732 0.055 Uiso 0.5 1 calc R . . . .
H6B H 0.5352 0.1211 0.1732 0.055 Uiso 0.5 1 calc R . . . .
C4 C 0.5530(4) 0.1579(4) 0.2823(4) 0.056(2) Uani 1 1 d . . . . .
H4 H 0.5892 0.1555 0.2616 0.068 Uiso 1 1 calc R . . . .
O1 O 0.6115(4) 0.1779(6) 0.4304(4) 0.112(3) Uani 1 1 d . U . . .
C2 C 0.5539(4) 0.1642(5) 0.3427(4) 0.065(3) Uani 1 1 d . . . . .
C1 C 0.6116(4) 0.1640(6) 0.3786(5) 0.081(3) Uani 1 1 d . . . . .
C3 C 0.5000 0.1699(10) 0.3750(7) 0.083(5) Uani 1 2 d S T P . .
H3 H 0.5000 0.159(9) 0.406(9) 0.100 Uiso 1 2 d RS T P . .
O6 O 0.5000 0.332(3) 0.275(3) 0.22(2) Uani 0.5 2 d S TU P . .
H6 H 0.5000 0.3667 0.2865 0.328 Uiso 0.5 2 calc RS T P . .


_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 O4 2.083(6) 22_554 ?
Mn1 O4 2.083(6) . ?
Mn1 O2 2.046(8) 7_665 ?
Mn1 O2 2.046(8) 13_545 ?
Mn3 O3 2.053(10) 22_554 ?
Mn3 O3 2.053(10) 26 ?
Mn3 O3 2.053(10) . ?
Mn3 O3 2.053(10) 45_665 ?
Mn2 P1 2.835(4) . ?
Mn2 O4 2.225(6) 28_655 ?
Mn2 O4 2.225(6) . ?
Mn2 O1 2.023(8) 32_565 ?
Mn2 O1 2.023(9) 7_665 ?
Mn2 O6 1.88(6) . ?
P1 O4 1.528(7) . ?
P1 O4 1.528(7) 28_655 ?
P1 O3 1.473(11) . ?
P1 C6 1.808(12) . ?
O2 Mn1 2.046(8) 10_656 ?
O2 C1 1.266(13) . ?
C5 C6 1.500(15) . ?
C5 C4 1.375(10) 28_655 ?
C5 C4 1.375(10) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C4 H4 0.9300 . ?
C4 C2 1.349(13) . ?
O1 Mn2 2.023(9) 10_656 ?
O1 C1 1.192(13) . ?
C2 C1 1.512(11) . ?
C2 C3 1.402(12) . ?
C3 C2 1.402(12) 28_655 ?
C3 H3 0.7(2) . ?
O6 H6 0.8200 . ?

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
O4 Mn1 O4 109.8(4) 22_554 . ?
O2 Mn1 O4 95.7(3) 7_665 22_554 ?
O2 Mn1 O4 92.2(3) 7_665 . ?
O2 Mn1 O4 95.7(3) 13_545 . ?
O2 Mn1 O4 92.2(3) 13_545 22_554 ?
O2 Mn1 O2 166.3(6) 7_665 13_545 ?
O3 Mn3 O3 108.5(3) . 22_554 ?
O3 Mn3 O3 108.5(3) 22_554 26 ?
O3 Mn3 O3 108.5(3) . 45_665 ?
O3 Mn3 O3 111.4(6) . 26 ?
O3 Mn3 O3 111.4(6) 22_554 45_665 ?
O3 Mn3 O3 108.5(3) 26 45_665 ?
O4 Mn2 P1 32.39(17) . . ?
O4 Mn2 P1 32.40(17) 28_655 . ?
O4 Mn2 O4 64.5(3) . 28_655 ?
O1 Mn2 P1 122.1(3) 32_565 . ?
O1 Mn2 P1 122.1(3) 7_665 . ?
O1 Mn2 O4 150.9(4) 7_665 28_655 ?
O1 Mn2 O4 150.9(4) 32_565 . ?
O1 Mn2 O4 93.3(3) 7_665 . ?
O1 Mn2 O4 93.3(3) 32_565 28_655 ?
O1 Mn2 O1 99.8(6) 7_665 32_565 ?
O6 Mn2 P1 113.2(19) . . ?
O6 Mn2 O4 106.8(16) . 28_655 ?
O6 Mn2 O4 106.8(16) . . ?
O6 Mn2 O1 97.3(12) . 32_565 ?
O6 Mn2 O1 97.3(12) . 7_665 ?
O4 P1 Mn2 51.3(2) 28_655 . ?
O4 P1 Mn2 51.3(2) . . ?
O4 P1 O4 101.9(5) . 28_655 ?
O4 P1 C6 107.7(4) . . ?
O4 P1 C6 107.7(4) 28_655 . ?
O3 P1 Mn2 126.2(5) . . ?
O3 P1 O4 115.2(4) . 28_655 ?
O3 P1 O4 115.2(4) . . ?
O3 P1 C6 108.6(6) . . ?
C6 P1 Mn2 125.3(4) . . ?
Mn1 O4 Mn2 125.8(3) . . ?
P1 O4 Mn1 134.9(4) . . ?
P1 O4 Mn2 96.3(3) . . ?
P1 O3 Mn3 132.2(7) . . ?
C1 O2 Mn1 143.0(7) . 10_656 ?
C4 C5 C6 121.0(5) . . ?
C4 C5 C6 121.0(5) 28_655 . ?
C4 C5 C4 117.8(11) . 28_655 ?
P1 C6 H6A 109.0 . . ?
P1 C6 H6B 109.0 . . ?
C5 C6 P1 113.1(8) . . ?
C5 C6 H6A 109.0 . . ?
C5 C6 H6B 109.0 . . ?
H6A C6 H6B 107.8 . . ?
C5 C4 H4 119.0 . . ?
C2 C4 C5 121.9(8) . . ?
C2 C4 H4 119.0 . . ?
C1 O1 Mn2 140.5(8) . 10_656 ?
C4 C2 C1 122.5(8) . . ?
C4 C2 C3 120.5(9) . . ?
C3 C2 C1 117.0(9) . . ?
O2 C1 C2 114.6(9) . . ?
O1 C1 O2 124.4(9) . . ?
O1 C1 C2 120.6(9) . . ?
C2 C3 C2 117.2(13) . 28_655 ?
C2 C3 H3 117(5) . . ?
C2 C3 H3 117(5) 28_655 . ?
Mn2 O6 H6 109.5 . . ?

_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.442
_oxdiff_exptl_absorpt_empirical_full_min 0.754
####################################################################### 
# 
# 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_20180311a1-1
_database_code_depnum_ccdc_archive 'CCDC 1865016'
_audit_update_record             
;
2018-09-17 deposited with the CCDC.
2019-01-11 downloaded from the CCDC.
;
_audit_creation_date             2018-09-15
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelxl_version_number           2013-2
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         '0.17(C216 H288 Mn54 O252 P24), H2 O2'
_chemical_formula_sum            'C36 H50 Mn9 O44 P4'
_chemical_formula_weight         1805.10
_chemical_melting_point          ?
_chemical_oxdiff_usercomment     'C H O'
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'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.2955 0.4335 '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      cubic
_space_group_IT_number           223
_space_group_name_H-M_alt        'P m -3 n'
_space_group_name_Hall           '-P 4n 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y+1/2, x+1/2, -z+1/2'
'-y+1/2, -x+1/2, -z+1/2'
'y+1/2, -x+1/2, z+1/2'
'-y+1/2, x+1/2, z+1/2'
'x+1/2, z+1/2, -y+1/2'
'-x+1/2, z+1/2, y+1/2'
'-x+1/2, -z+1/2, -y+1/2'
'x+1/2, -z+1/2, y+1/2'
'z+1/2, y+1/2, -x+1/2'
'z+1/2, -y+1/2, x+1/2'
'-z+1/2, y+1/2, x+1/2'
'-z+1/2, -y+1/2, -x+1/2'
'-x, -y, -z'
'x, y, -z'
'x, -y, z'
'-x, y, z'
'-z, -x, -y'
'-z, x, y'
'z, x, -y'
'z, -x, y'
'-y, -z, -x'
'y, -z, x'
'-y, z, x'
'y, z, -x'
'-y-1/2, -x-1/2, z-1/2'
'y-1/2, x-1/2, z-1/2'
'-y-1/2, x-1/2, -z-1/2'
'y-1/2, -x-1/2, -z-1/2'
'-x-1/2, -z-1/2, y-1/2'
'x-1/2, -z-1/2, -y-1/2'
'x-1/2, z-1/2, y-1/2'
'-x-1/2, z-1/2, -y-1/2'
'-z-1/2, -y-1/2, x-1/2'
'-z-1/2, y-1/2, -x-1/2'
'z-1/2, -y-1/2, -x-1/2'
'z-1/2, y-1/2, x-1/2'

_cell_length_a                   22.5987(2)
_cell_length_b                   22.5987(2)
_cell_length_c                   22.5987(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     11541.2(3)
_cell_formula_units_Z            6
_cell_measurement_reflns_used    9332
_cell_measurement_temperature    99.97(13)
_cell_measurement_theta_max      80.0610
_cell_measurement_theta_min      2.7650
_shelx_estimated_absorpt_T_max   0.178
_shelx_estimated_absorpt_T_min   0.178
_exptl_absorpt_coefficient_mu    13.182
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46498
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.558
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             5418
_exptl_crystal_preparation       ?
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0346
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 0.940
_diffrn_reflns_Laue_measured_fraction_max 1.001
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            22064
_diffrn_reflns_point_group_measured_fraction_full 0.940
_diffrn_reflns_point_group_measured_fraction_max 1.001
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         64.928
_diffrn_reflns_theta_min         2.765
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.940
_diffrn_measured_fraction_theta_max 1.001
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     20.00 117.00   0.50    2.00    --   49.30  57.00 -60.00  194
  2  ω    166.00 203.00   0.50   10.00    --  113.20  82.00   0.00   74
  3  ω    126.00 152.00   0.50   10.00    --  113.20  82.00   0.00   52
  4  ω     80.00 140.00   0.50   10.00    --  113.20  30.00-180.00  120
  5  ω     87.00 112.00   0.50   10.00    --  113.20  77.00 120.00   50
  6  ω    132.00 189.00   0.50   10.00    --  113.20  77.00 120.00  114
  7  ω     82.00 116.00   0.50   10.00    --  113.20  82.00   0.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0638512000
_diffrn_orient_matrix_UB_12      -0.0053503000
_diffrn_orient_matrix_UB_13      -0.0233615000
_diffrn_orient_matrix_UB_21      -0.0025785000
_diffrn_orient_matrix_UB_22      -0.0644421000
_diffrn_orient_matrix_UB_23      0.0221156000
_diffrn_orient_matrix_UB_31      -0.0237784000
_diffrn_orient_matrix_UB_32      0.0216533000
_diffrn_orient_matrix_UB_33      0.0600670000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1706
_reflns_number_total             1786
_reflns_odcompleteness_completeness 96.44
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     86.18
_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       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (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         0.945
_refine_diff_density_min         -2.001
_refine_diff_density_rms         0.138
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     134
_refine_ls_number_reflns         1786
_refine_ls_number_restraints     24
_refine_ls_R_factor_all          0.0614
_refine_ls_R_factor_gt           0.0595
_refine_ls_restrained_S_all      1.051
_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)+(0.1117P)²+52.3692P]
 where P=(Fo²+2Fc²)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1722
_refine_ls_wR_factor_ref         0.1752
_refine_special_details          
;
 ?
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
2. Restrained distances
 H7B_$2-H7B_$3
 2 with sigma of 0.01
 H7B_$4-H7B
 2 with sigma of 0.001
 H7B-H7B_$5
 2 with sigma of 0.001
 H7B_$6-H7B
 2 with sigma of 0.001
 H5B-Mn2
 2.531 with sigma of 0.001
 H5AA-Mn2
 2.531 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O5 \\sim O5A: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O5) \\sim Ueq, Uanis(O5A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Fixed Sof: H6A(0.5) H6B(0.5) H6C(0.5) H6D(0.5) O5(0.25) H5A(0.25) H5B(0.25)
 O5A(0.25) H5AA(0.25)
5.a Free rotating group:
 O5(H5A,H5B)
5.b Rotating group:
 O6(H6C,H6D), O7(H7A,H7B)
5.c Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
5.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4)
5.e Idealised tetrahedral OH refined as rotating group:
 O5A(H5AA)
;
_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
Mn1 Mn 0.14687(3) 0.2500 0.35313(3) 0.0148(3) Uani 1 2 d S T P . .
Mn2 Mn 0.17757(5) 0.33225(4) 0.5000 0.0236(4) Uani 1 2 d DS T P . .
P1 P 0.13982(7) 0.21216(7) 0.5000 0.0178(4) Uani 1 2 d S T P . .
Mn3 Mn 0.0000 0.2500 0.5000 0.0626(10) Uani 1 8 d S T P . .
O4 O 0.15625(14) 0.25018(13) 0.44606(13) 0.0214(7) Uani 1 1 d . . . . .
O3 O 0.0750(2) 0.1937(2) 0.5000 0.0320(11) Uani 1 2 d S T P . .
O2 O 0.3459(2) 0.1532(2) 0.34388(15) 0.0453(11) Uani 1 1 d . . . . .
O1 O 0.42676(17) 0.1835(3) 0.38971(16) 0.0581(14) Uani 1 1 d . . . . .
C5 C 0.2491(3) 0.1538(3) 0.5000 0.0200(14) Uani 1 2 d S T P . .
C2 C 0.3411(2) 0.1648(2) 0.44691(19) 0.0253(10) Uani 1 1 d . . . . .
C6 C 0.1829(3) 0.1445(3) 0.5000 0.0235(14) Uani 1 2 d S T P . .
H6A H 0.1722 0.1215 0.5346 0.028 Uiso 0.5 1 calc R . . . .
H6B H 0.1722 0.1215 0.4654 0.028 Uiso 0.5 1 calc R . . . .
C1 C 0.3739(2) 0.1670(2) 0.38887(19) 0.0258(11) Uani 1 1 d . . . . .
C3 C 0.3717(3) 0.1685(3) 0.5000 0.0247(14) Uani 1 2 d S T P . .
H3 H 0.4126 0.1734 0.5000 0.030 Uiso 1 2 calc RS T P . .
C4 C 0.2802(2) 0.15722(19) 0.44716(18) 0.0211(10) Uani 1 1 d . . . . .
H4 H 0.2600 0.1544 0.4114 0.025 Uiso 1 1 calc R . . . .
O6 O 0.0822(3) 0.3570(3) 0.5000 0.0550(17) Uani 1 2 d S T P . .
H6C H 0.0720 0.3982 0.4848 0.083 Uiso 0.5 1 d GR . . . .
H6D H 0.0617 0.3613 0.5404 0.083 Uiso 0.5 1 d GR . . . .
O7 O 0.14831(5) 0.24194(10) 0.2504(2) 0.0758(19) Uani 1 1 d . . . . .
H7A H 0.1497 0.2014 0.2335 0.114 Uiso 1 1 d GR . . . .
H7B H 0.1857 0.2567 0.2327 0.114 Uiso 1 1 d DGR . . . .
O5 O 0.2723(9) 0.3218(13) 0.5000 0.062(5) Uani 0.5 2 d S TU P . 1
H5A H 0.3042 0.3201 0.4801 0.092 Uiso 0.25 1 d G . . . 1
H5B H 0.2839 0.3262 0.5347 0.092 Uiso 0.25 1 d DG . . . 1
O5A O 0.2667(11) 0.3091(14) 0.5206(12) 0.055(5) Uani 0.25 1 d . U . A 2
H5AA H 0.2846 0.3382 0.5327 0.083 Uiso 0.25 1 calc DGR . . A 2


_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 O4 2.111(3) . ?
Mn1 O4 2.111(3) 24 ?
Mn1 O2 2.133(3) 19 ?
Mn1 O2 2.133(3) 9 ?
Mn1 O7 2.329(4) 24 ?
Mn1 O7 2.329(4) . ?
Mn2 P1 2.8447(18) . ?
Mn2 O4 2.271(3) . ?
Mn2 O4 2.271(3) 26_556 ?
Mn2 O1 2.108(4) 36_556 ?
Mn2 O1 2.108(4) 9 ?
Mn2 O6 2.226(6) . ?
Mn2 O5 2.15(2) . ?
P1 O4 1.537(3) . ?
P1 O4 1.537(3) 26_556 ?
P1 O3 1.524(5) . ?
P1 C6 1.812(7) . ?
Mn3 O3 2.118(5) . ?
Mn3 O3 2.118(5) 47_566 ?
Mn3 O3 2.118(5) 45_666 ?
Mn3 O3 2.118(5) 3_556 ?
O2 Mn1 2.133(3) 5 ?
O2 C1 1.238(6) . ?
O1 Mn2 2.108(4) 5 ?
O1 C1 1.251(7) . ?
C5 C6 1.510(10) . ?
C5 C4 1.389(6) . ?
C5 C4 1.389(6) 26_556 ?
C2 C1 1.507(6) . ?
C2 C3 1.388(6) . ?
C2 C4 1.386(7) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C3 C2 1.388(6) 26_556 ?
C3 H3 0.9300 . ?
C4 H4 0.9300 . ?
O6 H6C 1.0192 . ?
O6 H6D 1.0289 . ?
O7 H7A 0.9920 . ?
O7 H7B 0.9933 . ?
O5 H5A 0.8512 . ?
O5 H5B 0.8330 . ?
O5A O5A 0.93(6) 26_556 ?
O5A H5AA 0.8200 . ?

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
O4 Mn1 O4 101.52(18) . 24 ?
O4 Mn1 O2 93.89(14) 24 19 ?
O4 Mn1 O2 93.47(14) 24 9 ?
O4 Mn1 O2 93.47(14) . 19 ?
O4 Mn1 O2 93.89(14) . 9 ?
O4 Mn1 O7 172.12(10) 24 24 ?
O4 Mn1 O7 85.05(9) 24 . ?
O4 Mn1 O7 172.12(10) . . ?
O4 Mn1 O7 85.05(9) . 24 ?
O2 Mn1 O2 168.4(3) 19 9 ?
O2 Mn1 O7 81.65(14) 9 24 ?
O2 Mn1 O7 90.02(14) 19 24 ?
O2 Mn1 O7 90.02(14) 9 . ?
O2 Mn1 O7 81.65(14) 19 . ?
O7 Mn1 O7 88.76(6) 24 . ?
O4 Mn2 P1 32.58(8) 26_556 . ?
O4 Mn2 P1 32.58(8) . . ?
O4 Mn2 O4 64.92(15) 26_556 . ?
O1 Mn2 P1 127.35(11) 36_556 . ?
O1 Mn2 P1 127.35(11) 9 . ?
O1 Mn2 O4 95.45(13) 36_556 26_556 ?
O1 Mn2 O4 159.71(14) 9 26_556 ?
O1 Mn2 O4 95.45(13) 9 . ?
O1 Mn2 O4 159.71(14) 36_556 . ?
O1 Mn2 O1 103.5(2) 36_556 9 ?
O1 Mn2 O6 84.6(2) 9 . ?
O1 Mn2 O6 84.6(2) 36_556 . ?
O1 Mn2 O5 90.3(5) 9 . ?
O1 Mn2 O5 90.3(5) 36_556 . ?
O6 Mn2 P1 87.1(2) . . ?
O6 Mn2 O4 89.99(19) . . ?
O6 Mn2 O4 89.99(19) . 26_556 ?
O5 Mn2 P1 101.2(8) . . ?
O5 Mn2 O4 97.0(6) . . ?
O5 Mn2 O4 97.0(6) . 26_556 ?
O5 Mn2 O6 171.7(8) . . ?
O4 P1 Mn2 52.72(12) . . ?
O4 P1 Mn2 52.72(12) 26_556 . ?
O4 P1 O4 105.0(2) . 26_556 ?
O4 P1 C6 109.99(18) . . ?
O4 P1 C6 109.99(18) 26_556 . ?
O3 P1 Mn2 123.3(2) . . ?
O3 P1 O4 112.66(17) . 26_556 ?
O3 P1 O4 112.66(17) . . ?
O3 P1 C6 106.6(3) . . ?
C6 P1 Mn2 130.1(2) . . ?
O3 Mn3 O3 106.2(2) 45_666 47_566 ?
O3 Mn3 O3 111.13(13) 45_666 3_556 ?
O3 Mn3 O3 111.13(13) 47_566 . ?
O3 Mn3 O3 111.13(13) 3_556 47_566 ?
O3 Mn3 O3 111.13(13) 45_666 . ?
O3 Mn3 O3 106.2(2) 3_556 . ?
Mn1 O4 Mn2 123.84(13) . . ?
P1 O4 Mn1 139.81(18) . . ?
P1 O4 Mn2 94.70(15) . . ?
P1 O3 Mn3 127.2(3) . . ?
C1 O2 Mn1 142.6(4) . 5 ?
C1 O1 Mn2 136.1(3) . 5 ?
C4 C5 C6 120.7(3) 26_556 . ?
C4 C5 C6 120.7(3) . . ?
C4 C5 C4 118.6(6) 26_556 . ?
C3 C2 C1 120.3(5) . . ?
C4 C2 C1 119.7(4) . . ?
C4 C2 C3 119.9(5) . . ?
P1 C6 H6A 108.6 . . ?
P1 C6 H6B 108.6 . . ?
C5 C6 P1 114.5(4) . . ?
C5 C6 H6A 108.6 . . ?
C5 C6 H6B 108.6 . . ?
H6A C6 H6B 107.6 . . ?
O2 C1 O1 125.2(4) . . ?
O2 C1 C2 117.0(5) . . ?
O1 C1 C2 117.8(4) . . ?
C2 C3 C2 119.7(7) . 26_556 ?
C2 C3 H3 120.2 . . ?
C2 C3 H3 120.2 26_556 . ?
C5 C4 H4 119.5 . . ?
C2 C4 C5 120.9(4) . . ?
C2 C4 H4 119.5 . . ?
Mn2 O6 H6C 116.7 . . ?
Mn2 O6 H6D 117.3 . . ?
H6C O6 H6D 96.5 . . ?
Mn1 O7 H7A 117.1 . . ?
Mn1 O7 H7B 112.8 . . ?
H7A O7 H7B 97.4 . . ?
Mn2 O5 H5A 148.0 . . ?
Mn2 O5 H5B 107.5 . . ?
H5A O5 H5B 103.7 . . ?
O5A O5A H5AA 109.5 26_556 . ?

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 O2 C1 O1 -2.0(10) 5 . . . ?
Mn1 O2 C1 C2 176.7(5) 5 . . . ?
Mn2 P1 O4 Mn1 -164.4(4) . . . . ?
Mn2 P1 O3 Mn3 0.0 . . . . ?
Mn2 P1 C6 C5 0.0 . . . . ?
Mn2 O1 C1 O2 -19.0(10) 5 . . . ?
Mn2 O1 C1 C2 162.3(4) 5 . . . ?
O4 P1 O4 Mn1 -171.86(13) 26_556 . . . ?
O4 P1 O4 Mn2 -7.4(3) 26_556 . . . ?
O4 P1 O3 Mn3 59.26(16) 26_556 . . . ?
O4 P1 O3 Mn3 -59.27(16) . . . . ?
O4 P1 C6 C5 57.57(15) . . . . ?
O4 P1 C6 C5 -57.57(15) 26_556 . . . ?
O3 P1 O4 Mn1 -48.9(4) . . . . ?
O3 P1 O4 Mn2 115.5(2) . . . . ?
O3 P1 C6 C5 180.0 . . . . ?
C6 P1 O4 Mn1 69.9(4) . . . . ?
C6 P1 O4 Mn2 -125.7(2) . . . . ?
C6 P1 O3 Mn3 180.0 . . . . ?
C6 C5 C4 C2 -179.0(5) . . . . ?
C1 C2 C3 C2 -178.3(4) . . . 26_556 ?
C1 C2 C4 C5 178.6(4) . . . . ?
C3 C2 C1 O2 167.6(5) . . . . ?
C3 C2 C1 O1 -13.6(7) . . . . ?
C3 C2 C4 C5 0.6(8) . . . . ?
C4 C5 C6 P1 -91.0(5) . . . . ?
C4 C5 C6 P1 91.0(5) 26_556 . . . ?
C4 C5 C4 C2 -0.9(9) 26_556 . . . ?
C4 C2 C1 O2 -10.4(7) . . . . ?
C4 C2 C1 O1 168.4(5) . . . . ?
C4 C2 C3 C2 -0.2(10) . . . 26_556 ?

_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.795
_oxdiff_exptl_absorpt_empirical_full_min 0.688
