# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_RR-C4
_database_code_depnum_ccdc_archive 'CCDC 1864576'
_audit_update_record             
;
2018-08-29 deposited with the CCDC.
2018-10-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_chemical_name_systematic        ?
_chemical_name_common            work
_chemical_compound_source        synthesis
_exptl_crystal_recrystallization_method 'Dichloromethane and diethyl ether'
_chemical_melting_point          621.15
_chemical_formula_moiety         'C20 H30 F6 Mn N6 O6 S2'
_chemical_formula_sum            'C20 H30 F6 Mn N6 O6 S2'
_chemical_formula_weight         683.56

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'
F F 0.0171 0.0103 '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'
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'

_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_H-M_alt        'P 41 21 2'
_space_group_name_Hall           'P 4abw 2nw'

_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'
'-y+1/2, x+1/2, z+1/4'
'-x, -y, z+1/2'
'y+1/2, -x+1/2, z+3/4'
'x+1/2, -y+1/2, -z+3/4'
'-x+1/2, y+1/2, -z+1/4'
'y, x, -z'
'-y, -x, -z+1/2'

_cell_length_a                   9.3461(3)
_cell_length_b                   9.3461(3)
_cell_length_c                   32.8191(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2866.7(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    9922
_cell_measurement_theta_min      2.87
_cell_measurement_theta_max      24.75

_exptl_crystal_description       square
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.584
_exptl_crystal_F_000             1404
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.290
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.170
_exptl_absorpt_coefficient_mu    0.691
_shelx_estimated_absorpt_T_min   0.825
_shelx_estimated_absorpt_T_max   0.892
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.826
_exptl_absorpt_correction_T_max  0.852
_exptl_absorpt_process_details   'symmetry-related measurement'

_diffrn_ambient_temperature      173(2)
_diffrn_ambient_pressure         101.3
_diffrn_radiation_probe          x-ray
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_type              'Bruker SMART APEX'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            24894
_diffrn_reflns_av_unetI/netI     0.0212
_diffrn_reflns_av_R_equivalents  0.0337
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_theta_min         2.867
_diffrn_reflns_theta_max         25.541
_diffrn_reflns_theta_full        25.242
_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 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             2679
_reflns_number_gt                2393
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.629
_reflns_Friedel_fraction_max     1.000
_reflns_Friedel_fraction_full    1.000

_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.
;

_computing_data_collection       'APEX3 (Bruker, 2017)'
_computing_cell_refinement       'SAINT V8.37A (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.37A (Bruker, 2016)'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?
_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0869P)²+5.0972P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 868 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(9)
_chemical_absolute_configuration syn
_refine_ls_number_reflns         2678
_refine_ls_number_parameters     188
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0645
_refine_ls_R_factor_gt           0.0561
_refine_ls_wR_factor_ref         0.1646
_refine_ls_wR_factor_gt          0.1523
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_restrained_S_all      1.078
_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
Mn1 Mn 0.74365(9) 0.74365(9) 0.000000 0.0328(4) Uani 1 2 d S T P . .
S1 S 1.0255(2) 0.7816(2) 0.07078(6) 0.0572(6) Uani 1 1 d . . . . .
F1 F 1.0030(8) 1.0450(6) 0.0490(2) 0.110(2) Uani 1 1 d . . . . .
F2 F 1.1968(7) 0.9387(8) 0.02861(18) 0.105(2) Uani 1 1 d . . . . .
F3 F 1.1740(6) 1.0023(6) 0.09132(18) 0.0862(17) Uani 1 1 d . . . . .
O1 O 0.9467(6) 0.7479(7) 0.03439(15) 0.0645(16) Uani 1 1 d . . . . .
O2 O 1.1505(8) 0.6923(7) 0.0787(3) 0.093(2) Uani 1 1 d . . . . .
O3 O 0.9322(8) 0.8135(8) 0.10513(15) 0.084(2) Uani 1 1 d . . . . .
N1 N 0.6215(7) 0.8629(6) 0.04343(16) 0.0418(13) Uani 1 1 d . . . . .
N2 N 0.5098(6) 0.8830(6) 0.10150(16) 0.0387(13) Uani 1 1 d . . . . .
N3 N 0.6382(5) 0.5680(5) 0.04259(14) 0.0298(11) Uani 1 1 d . . . . .
C1 C 0.5812(9) 1.0034(7) 0.0489(2) 0.0523(19) Uani 1 1 d . . . . .
H1 H 0.598030 1.079075 0.030146 0.063 Uiso 1 1 calc R U . . .
C2 C 0.5141(8) 1.0161(7) 0.0850(2) 0.0494(17) Uani 1 1 d . . . . .
H2 H 0.476952 1.101473 0.096631 0.059 Uiso 1 1 calc R U . . .
C3 C 0.5764(7) 0.7937(7) 0.07524(17) 0.0370(14) Uani 1 1 d . . . . .
C4 C 0.4371(9) 0.8428(9) 0.1397(2) 0.0520(19) Uani 1 1 d . . . . .
H3A H 0.352434 0.785021 0.133448 0.078 Uiso 1 1 calc R U . . .
H3B H 0.407814 0.929564 0.154297 0.078 Uiso 1 1 calc R U . . .
H3C H 0.502685 0.787295 0.156826 0.078 Uiso 1 1 calc R U . . .
C5 C 0.6089(8) 0.6390(7) 0.08251(17) 0.0403(15) Uani 1 1 d . . . . .
H4A H 0.693417 0.629928 0.100531 0.048 Uiso 1 1 calc R U . . .
H4B H 0.526633 0.592247 0.096055 0.048 Uiso 1 1 calc R U . . .
C6 C 0.7427(8) 0.4511(7) 0.0490(2) 0.0453(15) Uani 1 1 d . . . . .
H5A H 0.834913 0.491698 0.057231 0.068 Uiso 1 1 calc R U . . .
H5B H 0.754560 0.397135 0.023631 0.068 Uiso 1 1 calc R U . . .
H5C H 0.707647 0.386950 0.070438 0.068 Uiso 1 1 calc R U . . .
C7 C 0.5019(6) 0.5199(6) 0.02326(15) 0.0269(11) Uani 1 1 d . . . . .
H6 H 0.430131 0.597800 0.027595 0.032 Uiso 1 1 calc R U . . .
C8 C 0.4409(8) 0.3842(7) 0.04287(19) 0.0396(15) Uani 1 1 d . . . . .
H7A H 0.513547 0.307285 0.041330 0.048 Uiso 1 1 calc R U . . .
H7B H 0.421620 0.403284 0.072026 0.048 Uiso 1 1 calc R U . . .
C9 C 0.3040(8) 0.3326(8) 0.0227(2) 0.0499(18) Uani 1 1 d . . . . .
H8A H 0.228408 0.406073 0.025639 0.060 Uiso 1 1 calc R U . . .
H8B H 0.270606 0.243763 0.036082 0.060 Uiso 1 1 calc R U . . .
C20 C 1.1032(9) 0.9531(10) 0.0587(3) 0.063(2) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Mn1 N1 2.139(5) . ?
Mn1 N1 2.139(5) 7 ?
Mn1 O1 2.208(5) . ?
Mn1 O1 2.208(5) 7 ?
Mn1 N3 2.371(5) 7 ?
Mn1 N3 2.371(5) . ?
S1 O1 1.439(5) . ?
S1 O3 1.456(7) . ?
S1 O2 1.459(7) . ?
S1 C20 1.803(9) . ?
F1 C20 1.310(11) . ?
F2 C20 1.327(10) . ?
F3 C20 1.339(9) . ?
N1 C3 1.298(8) . ?
N1 C1 1.378(9) . ?
N2 C3 1.351(8) . ?
N2 C2 1.358(9) . ?
N2 C4 1.475(8) . ?
N3 C6 1.480(8) . ?
N3 C7 1.492(7) . ?
N3 C5 1.494(7) . ?
C1 C2 1.347(10) . ?
C1 H1 0.9500 . ?
C2 H2 0.9500 . ?
C3 C5 1.497(9) . ?
C4 H3A 0.9800 . ?
C4 H3B 0.9800 . ?
C4 H3C 0.9800 . ?
C5 H4A 0.9900 . ?
C5 H4B 0.9900 . ?
C6 H5A 0.9800 . ?
C6 H5B 0.9800 . ?
C6 H5C 0.9800 . ?
C7 C8 1.532(8) . ?
C7 C7 1.545(10) 7 ?
C7 H6 1.0000 . ?
C8 C9 1.519(10) . ?
C8 H7A 0.9900 . ?
C8 H7B 0.9900 . ?
C9 C9 1.537(13) 7 ?
C9 H8A 0.9900 . ?
C9 H8B 0.9900 . ?

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 Mn1 N1 178.9(3) . 7 ?
N1 Mn1 O1 96.2(2) . . ?
N1 Mn1 O1 84.4(2) 7 . ?
N1 Mn1 O1 84.4(2) . 7 ?
N1 Mn1 O1 96.2(2) 7 7 ?
O1 Mn1 O1 103.3(3) . 7 ?
N1 Mn1 N3 103.9(2) . 7 ?
N1 Mn1 N3 75.28(18) 7 7 ?
O1 Mn1 N3 154.7(2) . 7 ?
O1 Mn1 N3 93.9(2) 7 7 ?
N1 Mn1 N3 75.28(18) . . ?
N1 Mn1 N3 103.9(2) 7 . ?
O1 Mn1 N3 93.9(2) . . ?
O1 Mn1 N3 154.7(2) 7 . ?
N3 Mn1 N3 76.8(2) 7 . ?
O1 S1 O3 112.4(4) . . ?
O1 S1 O2 115.6(4) . . ?
O3 S1 O2 117.3(5) . . ?
O1 S1 C20 102.7(4) . . ?
O3 S1 C20 103.3(4) . . ?
O2 S1 C20 103.0(4) . . ?
S1 O1 Mn1 150.3(4) . . ?
C3 N1 C1 106.4(6) . . ?
C3 N1 Mn1 116.7(4) . . ?
C1 N1 Mn1 136.8(5) . . ?
C3 N2 C2 107.3(5) . . ?
C3 N2 C4 126.7(6) . . ?
C2 N2 C4 125.9(6) . . ?
C6 N3 C7 113.7(5) . . ?
C6 N3 C5 108.9(5) . . ?
C7 N3 C5 110.5(5) . . ?
C6 N3 Mn1 108.7(4) . . ?
C7 N3 Mn1 108.2(3) . . ?
C5 N3 Mn1 106.6(3) . . ?
C2 C1 N1 109.0(6) . . ?
C2 C1 H1 125.5 . . ?
N1 C1 H1 125.5 . . ?
C1 C2 N2 106.5(6) . . ?
C1 C2 H2 126.8 . . ?
N2 C2 H2 126.8 . . ?
N1 C3 N2 110.8(6) . . ?
N1 C3 C5 122.9(6) . . ?
N2 C3 C5 126.0(5) . . ?
N2 C4 H3A 109.5 . . ?
N2 C4 H3B 109.5 . . ?
H3A C4 H3B 109.5 . . ?
N2 C4 H3C 109.5 . . ?
H3A C4 H3C 109.5 . . ?
H3B C4 H3C 109.5 . . ?
N3 C5 C3 109.0(5) . . ?
N3 C5 H4A 109.9 . . ?
C3 C5 H4A 109.9 . . ?
N3 C5 H4B 109.9 . . ?
C3 C5 H4B 109.9 . . ?
H4A C5 H4B 108.3 . . ?
N3 C6 H5A 109.5 . . ?
N3 C6 H5B 109.5 . . ?
H5A C6 H5B 109.5 . . ?
N3 C6 H5C 109.5 . . ?
H5A C6 H5C 109.5 . . ?
H5B C6 H5C 109.5 . . ?
N3 C7 C8 112.8(5) . . ?
N3 C7 C7 111.1(4) . 7 ?
C8 C7 C7 111.4(4) . 7 ?
N3 C7 H6 107.0 . . ?
C8 C7 H6 107.0 . . ?
C7 C7 H6 107.0 7 . ?
C9 C8 C7 113.1(5) . . ?
C9 C8 H7A 108.9 . . ?
C7 C8 H7A 108.9 . . ?
C9 C8 H7B 108.9 . . ?
C7 C8 H7B 108.9 . . ?
H7A C8 H7B 107.8 . . ?
C8 C9 C9 109.3(5) . 7 ?
C8 C9 H8A 109.8 . . ?
C9 C9 H8A 109.8 7 . ?
C8 C9 H8B 109.8 . . ?
C9 C9 H8B 109.8 7 . ?
H8A C9 H8B 108.3 . . ?
F1 C20 F2 110.8(8) . . ?
F1 C20 F3 108.9(8) . . ?
F2 C20 F3 107.7(7) . . ?
F1 C20 S1 110.4(6) . . ?
F2 C20 S1 109.8(7) . . ?
F3 C20 S1 109.2(6) . . ?

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
O3 S1 O1 Mn1 13.3(10) . . . . ?
O2 S1 O1 Mn1 151.6(8) . . . . ?
C20 S1 O1 Mn1 -97.0(8) . . . . ?
C3 N1 C1 C2 1.3(9) . . . . ?
Mn1 N1 C1 C2 -174.0(6) . . . . ?
N1 C1 C2 N2 -1.4(9) . . . . ?
C3 N2 C2 C1 0.9(9) . . . . ?
C4 N2 C2 C1 -175.3(7) . . . . ?
C1 N1 C3 N2 -0.7(8) . . . . ?
Mn1 N1 C3 N2 175.7(4) . . . . ?
C1 N1 C3 C5 -175.1(6) . . . . ?
Mn1 N1 C3 C5 1.2(8) . . . . ?
C2 N2 C3 N1 -0.1(8) . . . . ?
C4 N2 C3 N1 176.1(6) . . . . ?
C2 N2 C3 C5 174.1(7) . . . . ?
C4 N2 C3 C5 -9.7(11) . . . . ?
C6 N3 C5 C3 148.7(5) . . . . ?
C7 N3 C5 C3 -85.8(6) . . . . ?
Mn1 N3 C5 C3 31.6(6) . . . . ?
N1 C3 C5 N3 -24.7(9) . . . . ?
N2 C3 C5 N3 161.7(6) . . . . ?
C6 N3 C7 C8 46.5(6) . . . . ?
C5 N3 C7 C8 -76.3(6) . . . . ?
Mn1 N3 C7 C8 167.4(4) . . . . ?
C6 N3 C7 C7 -79.5(6) . . . 7 ?
C5 N3 C7 C7 157.8(5) . . . 7 ?
Mn1 N3 C7 C7 41.4(6) . . . 7 ?
N3 C7 C8 C9 -178.6(5) . . . . ?
C7 C7 C8 C9 -52.9(8) 7 . . . ?
C7 C8 C9 C9 58.1(9) . . . 7 ?
O1 S1 C20 F1 56.7(7) . . . . ?
O3 S1 C20 F1 -60.2(7) . . . . ?
O2 S1 C20 F1 177.2(7) . . . . ?
O1 S1 C20 F2 -65.7(7) . . . . ?
O3 S1 C20 F2 177.3(6) . . . . ?
O2 S1 C20 F2 54.7(7) . . . . ?
O1 S1 C20 F3 176.4(6) . . . . ?
O3 S1 C20 F3 59.4(7) . . . . ?
O2 S1 C20 F3 -63.2(7) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C4 H3B O2 0.98 2.58 3.523(11) 162.4 6_655

_refine_diff_density_max         1.491
_refine_diff_density_min         -0.625
_refine_diff_density_rms         0.084

####################################################################### 
# 
# 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_SS-C4
_database_code_depnum_ccdc_archive 'CCDC 1864577'
_audit_update_record             
;
2018-08-29 deposited with the CCDC.
2018-10-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_chemical_name_systematic        ?
_chemical_name_common            S,S-C4
_chemical_compound_source        synthesis
_chemical_melting_point          618.15
_chemical_formula_moiety         'C20 H30 F6 Mn N6 O6 S2'
_chemical_formula_sum            'C20 H30 F6 Mn N6 O6 S2'
_chemical_formula_weight         683.56

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'
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'
F F 0.0171 0.0103 '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'

_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_H-M_alt        'P 43 21 2'
_space_group_name_Hall           'P 4nw 2abw'

_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'
'-y+1/2, x+1/2, z+3/4'
'-x, -y, z+1/2'
'y+1/2, -x+1/2, z+1/4'
'x+1/2, -y+1/2, -z+1/4'
'-x+1/2, y+1/2, -z+3/4'
'y, x, -z'
'-y, -x, -z+1/2'

_cell_length_a                   9.348(2)
_cell_length_b                   9.348(2)
_cell_length_c                   32.8311(15)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2868.83(18)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1556
_cell_measurement_theta_min      2.3
_cell_measurement_theta_max      25.0

_exptl_crystal_description       Prism
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.583
_exptl_crystal_F_000             1404.0
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    0.691
_shelx_estimated_absorpt_T_min   0.608
_shelx_estimated_absorpt_T_max   0.608
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.81
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_process_details   'symmetry-related measurement'

_diffrn_ambient_temperature      293(2)
_diffrn_ambient_pressure         101.3
_diffrn_radiation_wavelength     0.71075
_diffrn_radiation_type           MoK\a
_diffrn_radiation_probe          x-ray
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_type              'Bruker SMART APEX'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            24522
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_av_R_equivalents  0.0574
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_theta_min         2.265
_diffrn_reflns_theta_max         25.038
_diffrn_reflns_theta_full        25.038
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2522
_reflns_number_gt                2069
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.621
_reflns_Friedel_fraction_max     1.000
_reflns_Friedel_fraction_full    1.000

_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.
;

_computing_data_collection       'APEX3 (Bruker, 2017)'
_computing_cell_refinement       'SAINT V8.37A (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.37A (Bruker, 2016)'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_molecular_graphics    
'X-Seed (Barbour, 2001; Atwood & Barbour, 2003)'
_computing_publication_material  ?
_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0707P)²+6.3135P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 703 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(14)
_chemical_absolute_configuration syn
_refine_ls_number_reflns         2517
_refine_ls_number_parameters     188
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0761
_refine_ls_R_factor_gt           0.0555
_refine_ls_wR_factor_ref         0.1573
_refine_ls_wR_factor_gt          0.1380
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_restrained_S_all      1.056
_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
Mn1 Mn 0.25621(10) 0.74379(10) 0.250000 0.0347(4) Uani 1 2 d S T P . .
S1 S -0.0249(3) 0.7820(2) 0.32078(6) 0.0616(7) Uani 1 1 d . . . . .
N1 N 0.4903(7) 0.8832(6) 0.35149(17) 0.0397(14) Uani 1 1 d . . . . .
N3 N 0.3618(6) 0.5683(6) 0.29262(15) 0.0312(13) Uani 1 1 d . . . . .
F2 F -0.1739(7) 1.0015(7) 0.34133(18) 0.0890(19) Uani 1 1 d . . . . .
N2 N 0.3782(7) 0.8631(6) 0.29334(17) 0.0441(15) Uani 1 1 d . . . . .
F1 F -0.0022(8) 1.0443(6) 0.2988(2) 0.112(3) Uani 1 1 d . . . . .
O1 O 0.0536(6) 0.7482(8) 0.28434(15) 0.0660(17) Uani 1 1 d . . . . .
C9 C 0.6963(9) 0.3330(9) 0.2728(2) 0.052(2) Uani 1 1 d . . . . .
H9A H 0.729512 0.246177 0.285920 0.063 Uiso 1 1 calc R U . . .
H9B H 0.770149 0.405245 0.275504 0.063 Uiso 1 1 calc R U . . .
F3 F -0.1972(8) 0.9381(8) 0.27868(19) 0.107(2) Uani 1 1 d . . . . .
O3 O 0.0678(8) 0.8134(8) 0.35532(16) 0.084(2) Uani 1 1 d . . . . .
C8 C 0.5597(9) 0.3841(7) 0.2928(2) 0.0412(17) Uani 1 1 d . . . . .
H8A H 0.578535 0.402867 0.321381 0.049 Uiso 1 1 calc R U . . .
H8B H 0.488799 0.308457 0.291340 0.049 Uiso 1 1 calc R U . . .
C3 C 0.4235(8) 0.7936(8) 0.32527(19) 0.0379(16) Uani 1 1 d . . . . .
C2 C 0.4854(9) 1.0173(8) 0.3349(2) 0.0506(19) Uani 1 1 d . . . . .
H2 H 0.521109 1.101130 0.346316 0.061 Uiso 1 1 calc R U . . .
C1 C 0.4184(10) 1.0035(8) 0.2988(2) 0.052(2) Uani 1 1 d . . . . .
H1 H 0.401894 1.077332 0.280470 0.062 Uiso 1 1 calc R U . . .
C7 C 0.4980(7) 0.5196(7) 0.27323(17) 0.0298(13) Uani 1 1 d . . . . .
H7 H 0.568372 0.595879 0.277466 0.036 Uiso 1 1 calc R U . . .
C6 C 0.2582(9) 0.4503(8) 0.2989(2) 0.0476(18) Uani 1 1 d . . . . .
H6A H 0.247014 0.397668 0.274045 0.071 Uiso 1 1 calc R U . . .
H6B H 0.167531 0.489259 0.307028 0.071 Uiso 1 1 calc R U . . .
H6C H 0.293031 0.387569 0.319872 0.071 Uiso 1 1 calc R U . . .
O2 O -0.1491(8) 0.6923(7) 0.3288(3) 0.095(3) Uani 1 1 d . . . . .
C4 C 0.3913(9) 0.6386(8) 0.33256(18) 0.0425(18) Uani 1 1 d . . . . .
H4A H 0.472133 0.592804 0.345720 0.051 Uiso 1 1 calc R U . . .
H4B H 0.308696 0.629433 0.350262 0.051 Uiso 1 1 calc R U . . .
C5 C 0.5628(10) 0.8430(10) 0.3896(2) 0.055(2) Uani 1 1 d . . . . .
H5A H 0.497556 0.791279 0.406696 0.083 Uiso 1 1 calc R U . . .
H5B H 0.594367 0.927743 0.403437 0.083 Uiso 1 1 calc R U . . .
H5C H 0.643891 0.783674 0.383471 0.083 Uiso 1 1 calc R U . . .
C10 C -0.1019(11) 0.9510(11) 0.3087(3) 0.065(3) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Mn1 N2 2.138(6) . ?
Mn1 N2 2.138(6) 8_665 ?
Mn1 O1 2.205(5) 8_665 ?
Mn1 O1 2.205(5) . ?
Mn1 N3 2.371(5) 8_665 ?
Mn1 N3 2.371(5) . ?
S1 O1 1.439(5) . ?
S1 O2 1.457(7) . ?
S1 O3 1.457(7) . ?
S1 C10 1.780(10) . ?
N1 C3 1.354(9) . ?
N1 C2 1.367(10) . ?
N1 C5 1.471(9) . ?
N3 C6 1.483(9) . ?
N3 C7 1.494(8) . ?
N3 C4 1.492(8) . ?
F2 C10 1.350(10) . ?
N2 C3 1.304(9) . ?
N2 C1 1.376(10) . ?
F1 C10 1.317(11) . ?
C9 C8 1.515(11) . ?
C9 C9 1.544(14) 8_665 ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
F3 C10 1.334(11) . ?
C8 C7 1.533(9) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C3 C4 1.499(11) . ?
C2 C1 1.347(10) . ?
C2 H2 0.9300 . ?
C1 H1 0.9300 . ?
C7 C7 1.543(11) 8_665 ?
C7 H7 0.9800 . ?
C6 H6A 0.9600 . ?
C6 H6B 0.9600 . ?
C6 H6C 0.9600 . ?
C4 H4A 0.9700 . ?
C4 H4B 0.9700 . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?

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
N2 Mn1 N2 179.1(3) . 8_665 ?
N2 Mn1 O1 84.4(2) . 8_665 ?
N2 Mn1 O1 96.2(2) 8_665 8_665 ?
N2 Mn1 O1 96.2(2) . . ?
N2 Mn1 O1 84.4(2) 8_665 . ?
O1 Mn1 O1 103.3(4) 8_665 . ?
N2 Mn1 N3 104.0(2) . 8_665 ?
N2 Mn1 N3 75.3(2) 8_665 8_665 ?
O1 Mn1 N3 94.0(2) 8_665 8_665 ?
O1 Mn1 N3 154.7(2) . 8_665 ?
N2 Mn1 N3 75.3(2) . . ?
N2 Mn1 N3 104.0(2) 8_665 . ?
O1 Mn1 N3 154.7(2) 8_665 . ?
O1 Mn1 N3 94.0(2) . . ?
N3 Mn1 N3 76.8(3) 8_665 . ?
O1 S1 O2 115.5(4) . . ?
O1 S1 O3 112.8(4) . . ?
O2 S1 O3 116.7(5) . . ?
O1 S1 C10 102.5(4) . . ?
O2 S1 C10 103.2(5) . . ?
O3 S1 C10 103.6(5) . . ?
C3 N1 C2 107.4(6) . . ?
C3 N1 C5 126.5(6) . . ?
C2 N1 C5 126.0(6) . . ?
C6 N3 C7 112.9(5) . . ?
C6 N3 C4 109.0(5) . . ?
C7 N3 C4 110.6(5) . . ?
C6 N3 Mn1 109.0(4) . . ?
C7 N3 Mn1 108.3(3) . . ?
C4 N3 Mn1 106.9(4) . . ?
C3 N2 C1 106.3(6) . . ?
C3 N2 Mn1 116.6(5) . . ?
C1 N2 Mn1 136.9(5) . . ?
S1 O1 Mn1 150.2(4) . . ?
C8 C9 C9 109.1(6) . 8_665 ?
C8 C9 H9A 109.9 . . ?
C9 C9 H9A 109.9 8_665 . ?
C8 C9 H9B 109.9 . . ?
C9 C9 H9B 109.9 8_665 . ?
H9A C9 H9B 108.3 . . ?
C9 C8 C7 113.3(6) . . ?
C9 C8 H8A 108.9 . . ?
C7 C8 H8A 108.9 . . ?
C9 C8 H8B 108.9 . . ?
C7 C8 H8B 108.9 . . ?
H8A C8 H8B 107.7 . . ?
N2 C3 N1 110.7(6) . . ?
N2 C3 C4 123.0(6) . . ?
N1 C3 C4 126.1(6) . . ?
C1 C2 N1 106.1(7) . . ?
C1 C2 H2 127.0 . . ?
N1 C2 H2 127.0 . . ?
C2 C1 N2 109.5(7) . . ?
C2 C1 H1 125.2 . . ?
N2 C1 H1 125.2 . . ?
N3 C7 C8 113.2(5) . . ?
N3 C7 C7 111.3(4) . 8_665 ?
C8 C7 C7 111.5(4) . 8_665 ?
N3 C7 H7 106.8 . . ?
C8 C7 H7 106.8 . . ?
C7 C7 H7 106.8 8_665 . ?
N3 C6 H6A 109.5 . . ?
N3 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
N3 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
N3 C4 C3 108.8(5) . . ?
N3 C4 H4A 109.9 . . ?
C3 C4 H4A 109.9 . . ?
N3 C4 H4B 109.9 . . ?
C3 C4 H4B 109.9 . . ?
H4A C4 H4B 108.3 . . ?
N1 C5 H5A 109.5 . . ?
N1 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
N1 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
F1 C10 F3 110.5(9) . . ?
F1 C10 F2 108.5(8) . . ?
F3 C10 F2 106.5(8) . . ?
F1 C10 S1 110.9(7) . . ?
F3 C10 S1 110.8(7) . . ?
F2 C10 S1 109.6(7) . . ?

_refine_diff_density_max         1.244
_refine_diff_density_min         -0.577
_refine_diff_density_rms         0.076

