# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_Mn4S
_database_code_depnum_ccdc_archive 'CCDC 1818795'
_audit_update_record             
;
2018-01-23 deposited with the CCDC.
2018-09-13 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C72 Mn12  O48 S3'
_chemical_formula_sum            'C72 Mn12  O48 S3'
_chemical_formula_weight         2388.18

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'
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'
S S 0.1246 0.1234 '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'
In In -0.7276 1.3100 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_H-M_alt        'P m -3 m'
_space_group_name_Hall           '-P 4 2 3'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -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, x, -z'
'-y, -x, -z'
'y, -x, z'
'-y, x, z'
'x, z, -y'
'-x, z, y'
'-x, -z, -y'
'x, -z, y'
'z, y, -x'
'z, -y, x'
'-z, y, x'
'-z, -y, -x'
'-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, -x, z'
'y, x, z'
'-y, x, -z'
'y, -x, -z'
'-x, -z, y'
'x, -z, -y'
'x, z, y'
'-x, z, -y'
'-z, -y, x'
'-z, y, -x'
'z, -y, -x'
'z, y, x'

_cell_length_a                   15.8573(6)
_cell_length_b                   15.8573(6)
_cell_length_c                   15.8573(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3987.4(5)
_cell_formula_units_Z            1
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    4011
_cell_measurement_theta_min      2.57
_cell_measurement_theta_max      24.45

_exptl_crystal_description       cubic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    0.995
_exptl_crystal_F_000             3219
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_exptl_absorpt_coefficient_mu    1.009
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.886
_exptl_absorpt_correction_T_max  0.886
_exptl_absorpt_process_details   
;
Bruker: SADABS v2012/1, Bruker AXS Inc., 
Madison, Wisconsin, USA, 2012.
;
_exptl_absorpt_special_details   
;Department of Chemistry 
University of Anywhere 
Sometown 
Somewhere, UK 
;


_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'fine-focus sealed tube'
_diffrn_measurement_method       'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean '\f and \w scans'
_diffrn_reflns_number            11737
_diffrn_reflns_av_unetI/netI     0.0176
_diffrn_reflns_av_R_equivalents  0.0603
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.872
_diffrn_reflns_theta_max         24.674
_diffrn_reflns_theta_full        24.674
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.995
_reflns_number_total             741
_reflns_number_gt                666
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;

_computing_data_collection       
;

Bruker: Bruker Instrument Service v3.0.26, Bruker AXS Inc., 
Madison, Wisconsin?? USA, 2012.
;
_computing_cell_refinement       
;

Bruker: APEX2 v2013.10-0, Bruker AXS Inc., 
Madison, Wisconsin, USA, 2012.
;
_computing_data_reduction        
;

Bruker: SAINT V8.27B, Bruker AXS Inc., 
Madison, Wisconsin, USA, 2012.
;
_computing_structure_solution    
;
SIR97 ( A. Altomare, M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, 
A. Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna,J. Appl.  Crystallogr. 1999, 32, 115-119.)
;
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    
;

K. Brandenburg, H. Putz: 
Diamond - Crystal and Molecular Structure Visualization v3.2i, 
Crystal Impact GbR, Bonn, Germany, 2012
'

;
_computing_publication_material  
;

WinGX publication routines (L. Farrugia, 
J. Appl. Crystallogr. 1999, 32, 837-838.)
;
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0600P)²+5.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         741
_refine_ls_number_parameters     34
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0347
_refine_ls_wR_factor_ref         0.1004
_refine_ls_wR_factor_gt          0.0980
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_restrained_S_all      1.019
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C3 C 0.26463(16) 0.26463(16) 0.1574(2) 0.0280(8) Uani 1 2 d S T P . .
Mn1 Mn 0.0000 0.5000 0.15384(4) 0.0179(3) Uani 1 4 d S T P . .
S1 S 0.0000 0.5000 0.0000 0.0498(10) Uani 1 16 d S T P . .
C1 C 0.15365(16) 0.3780(2) 0.15365(16) 0.0297(8) Uani 1 2 d S T P . .
O1 O 0.08958(12) 0.40694(13) 0.18885(13) 0.0472(6) Uani 1 1 d . . . . .
C2 C 0.19308(15) 0.3004(2) 0.19308(15) 0.0262(8) Uani 1 2 d S 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
C3 C2 1.389(2) 9 ?
C3 C2 1.389(2) . ?
Mn1 O1 2.1223(18) . ?
Mn1 O1 2.1223(18) 27_565 ?
Mn1 O1 2.1223(18) 28 ?
Mn1 O1 2.1223(18) 2_565 ?
Mn1 S1 2.4395(7) . ?
S1 Mn1 2.4394(7) 45_565 ?
S1 Mn1 2.4394(7) 21 ?
S1 Mn1 2.4394(7) 25_565 ?
C1 O1 1.246(2) 48 ?
C1 O1 1.246(2) . ?
C1 C2 1.515(4) . ?
C2 C3 1.389(2) 5 ?

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
C2 C3 C2 120.1(3) 9 . ?
O1 Mn1 O1 88.11(12) . 27_565 ?
O1 Mn1 O1 84.04(11) . 28 ?
O1 Mn1 O1 149.67(12) 27_565 28 ?
O1 Mn1 O1 149.67(12) . 2_565 ?
O1 Mn1 O1 84.04(11) 27_565 2_565 ?
O1 Mn1 O1 88.11(12) 28 2_565 ?
O1 Mn1 S1 105.17(6) . . ?
O1 Mn1 S1 105.16(6) 27_565 . ?
O1 Mn1 S1 105.16(6) 28 . ?
O1 Mn1 S1 105.16(6) 2_565 . ?
Mn1 S1 Mn1 180.0 45_565 21 ?
Mn1 S1 Mn1 90.0 45_565 25_565 ?
Mn1 S1 Mn1 90.0 21 25_565 ?
Mn1 S1 Mn1 90.0 45_565 . ?
Mn1 S1 Mn1 90.0 21 . ?
Mn1 S1 Mn1 180.0 25_565 . ?
O1 C1 O1 126.5(3) 48 . ?
O1 C1 C2 116.75(16) 48 . ?
O1 C1 C2 116.75(16) . . ?
C1 O1 Mn1 133.16(19) . . ?
C3 C2 C3 119.9(3) . 5 ?
C3 C2 C1 120.07(16) . . ?
C3 C2 C1 120.07(16) 5 . ?

_refine_diff_density_max         0.723
_refine_diff_density_min         -0.332
_refine_diff_density_rms         0.071



