# Electronic Supplementary Material (ESI) for Chemical Science.
# 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_2
_database_code_depnum_ccdc_archive 'CCDC 1894228'
loop_
_audit_author_name
_audit_author_address
'Lujia Liu'
;Northwestern University
United States of America
;
_audit_update_record             
;
2019-01-28 deposited with the CCDC.	2019-03-14 downloaded from the CCDC.
;
_audit_creation_date             2018-08-24
_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         'C18 Cl6 Mn2 O12, 2(C2 H6 N0.5)'
_chemical_formula_sum            'C22 H12 Cl6 Mn2 N O12'
_chemical_formula_weight         804.94
_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'
Cl Cl 0.1484 0.1585 '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'

_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      trigonal
_space_group_IT_number           162
_space_group_name_H-M_alt        'P -3 1 m'
_space_group_name_Hall           '-P 3 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-y, -x, -z'
'-x+y, y, -z'
'x, x-y, -z'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'y, x, z'
'x-y, -y, z'
'-x, -x+y, z'

_cell_length_a                   14.0833(13)
_cell_length_b                   14.0833(13)
_cell_length_c                   10.0253(12)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1722.0(4)
_cell_formula_units_Z            0.99996
_cell_measurement_reflns_used    6047
_cell_measurement_temperature    250(2)
_cell_measurement_theta_max      25.62
_cell_measurement_theta_min      2.63
_shelx_estimated_absorpt_T_max   0.983
_shelx_estimated_absorpt_T_min   0.933
_exptl_absorpt_coefficient_mu    0.626
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5304
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1226 before and 0.0736 after correction. The Ratio of minimum to maximum transmission is 0.7117. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    0.776
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             399
_exptl_crystal_size_max          0.113
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.027
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1063
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            13161
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        23.248
_diffrn_reflns_theta_max         23.248
_diffrn_reflns_theta_min         2.630
_diffrn_ambient_temperature      250.02
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                544
_reflns_number_total             897
_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 V8.38A (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.537
_refine_diff_density_min         -0.578
_refine_diff_density_rms         0.143
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.518
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     47
_refine_ls_number_reflns         897
_refine_ls_number_restraints     18
_refine_ls_R_factor_all          0.1725
_refine_ls_R_factor_gt           0.1305
_refine_ls_restrained_S_all      1.504
_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)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3529
_refine_ls_wR_factor_ref         0.4018
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C3
 1.49 with sigma of 0.01
 N1-C3 \\sim N1-C4
 with sigma of 0.01
 C3-C4_$1 \\sim C4_$1-C4
 with sigma of 0.01
3. Rigid bond restraints
 N1, C3, N1, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C4 \\sim N1 \\sim C3: within 2A with sigma of 0.002 and sigma for terminal
atoms of 0.004
5. Others
 Fixed Sof: N1(0.08333) C3(0.08333) H3B(0.08333) H3A(0.08333) H3C(0.08333)
 C4(0.25) H4A(0.25) H4B(0.25) H4C(0.25)
6.a Me refined with riding coordinates:
 C3(H3B,H3A,H3C), C4(H4A,H4B,H4C)
;
_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
Mn1 Mn 0.666667 0.333333 0.000000 0.0626(14) Uani 1 6 d S T P . .
Cl1 Cl 1.000000 0.6033(3) 0.2823(4) 0.1064(19) Uani 1 2 d S T P . .
O1 O 0.8082(4) 0.4460(5) 0.1176(5) 0.0713(19) Uani 1 1 d . . . . .
C1 C 0.8997(6) 0.4737(6) 0.0678(6) 0.053(2) Uani 1 1 d . . . . .
C2 C 1.000000 0.5489(7) 0.1304(9) 0.057(3) Uani 1 2 d S T P . .
N1 N 0.666667 0.333333 0.500000 0.130(12) Uani 0.5 6 d DS TU P . .
C3 C 0.666667 0.333333 0.3514(10) 0.130(12) Uani 0.25 3 d DS TU P B .
H3B H 0.673006 0.401207 0.319176 0.196 Uiso 0.0833 1 calc R . . A -1
H3A H 0.728202 0.326994 0.319176 0.196 Uiso 0.0833 1 calc R . . A -1
H3C H 0.598793 0.271799 0.319176 0.196 Uiso 0.0833 1 calc R . . A -1
C4 C 0.657(4) 0.229(2) 0.5511(13) 0.133(12) Uani 0.25 1 d D U . B -1
H4A H 0.652626 0.183017 0.476450 0.199 Uiso 0.25 1 calc R . . B -1
H4B H 0.720585 0.245434 0.605030 0.199 Uiso 0.25 1 calc R . . B -1
H4C H 0.591176 0.190239 0.605033 0.199 Uiso 0.25 1 calc R . . B -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
Mn1 O1 2.173(6) 6 ?
Mn1 O1 2.173(6) 5_655 ?
Mn1 O1 2.173(6) . ?
Mn1 O1 2.173(6) 3_665 ?
Mn1 O1 2.173(6) 2_655 ?
Mn1 O1 2.173(6) 4_665 ?
Cl1 C2 1.705(10) . ?
O1 C1 1.249(8) . ?
C1 C1 1.516(13) 6 ?
C1 C2 1.420(9) . ?
N1 C3 1.489(10) . ?
N1 C3 1.489(10) 4_666 ?
N1 C4 1.499(14) . ?
N1 C4 1.499(14) 3_665 ?

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
O1 Mn1 O1 101.5(3) 6 3_665 ?
O1 Mn1 O1 93.33(19) 4_665 5_655 ?
O1 Mn1 O1 101.5(3) 4_665 2_655 ?
O1 Mn1 O1 93.33(19) 6 4_665 ?
O1 Mn1 O1 161.4(3) 6 2_655 ?
O1 Mn1 O1 74.8(3) 3_665 4_665 ?
O1 Mn1 O1 161.4(3) 3_665 5_655 ?
O1 Mn1 O1 74.8(3) 6 . ?
O1 Mn1 O1 101.5(3) . 5_655 ?
O1 Mn1 O1 93.33(19) 3_665 . ?
O1 Mn1 O1 93.33(19) 3_665 2_655 ?
O1 Mn1 O1 161.4(3) 4_665 . ?
O1 Mn1 O1 74.8(3) 5_655 2_655 ?
O1 Mn1 O1 93.33(19) 6 5_655 ?
O1 Mn1 O1 93.33(19) . 2_655 ?
C1 O1 Mn1 115.9(4) . . ?
O1 C1 C1 116.7(4) . 6 ?
O1 C1 C2 122.9(6) . . ?
C2 C1 C1 120.4(4) . 6 ?
C1 C2 Cl1 120.4(4) . . ?
C1 C2 Cl1 120.4(4) 12_765 . ?
C1 C2 C1 119.0(9) . 12_765 ?
C3 N1 C3 180.0 4_666 . ?
C3 N1 C4 70.0(4) 4_666 3_665 ?
C3 N1 C4 70.0(4) 4_666 . ?
C3 N1 C4 110.0(4) . 3_665 ?
C3 N1 C4 110.0(4) . . ?
C4 N1 C4 108.9(4) . 3_665 ?

_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 0.000 0.000 -0.244 962.7 190.1 ?

_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_3
_database_code_depnum_ccdc_archive 'CCDC 1894229'
loop_
_audit_author_name
_audit_author_address
'Lujia Liu'
;Northwestern University
United States of America
;
_audit_update_record             
;
2019-01-28 deposited with the CCDC.	2019-03-14 downloaded from the CCDC.
;
_audit_creation_date             2018-08-24
_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         'C18 Cl6 Mn2 O12, 2(C4 H12 N1)'
_chemical_formula_sum            'C26 H24 Cl6 Mn2 N2 O12'
_chemical_formula_weight         879.09
_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'
Cl Cl 0.1484 0.1585 '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'

_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      trigonal
_space_group_IT_number           162
_space_group_name_H-M_alt        'P -3 1 m'
_space_group_name_Hall           '-P 3 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-y, -x, -z'
'-x+y, y, -z'
'x, x-y, -z'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'y, x, z'
'x-y, -y, z'
'-x, -x+y, z'

_cell_length_a                   14.030(3)
_cell_length_b                   14.030(3)
_cell_length_c                   9.3030(19)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1585.9(8)
_cell_formula_units_Z            0.99996
_cell_measurement_reflns_used    1764
_cell_measurement_temperature    250(2)
_cell_measurement_theta_max      18.78
_cell_measurement_theta_min      2.90
_shelx_estimated_absorpt_T_max   0.952
_shelx_estimated_absorpt_T_min   0.904
_exptl_absorpt_coefficient_mu    0.684
_exptl_absorpt_correction_T_max  0.7443
_exptl_absorpt_correction_T_min  0.6032
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0963 before and 0.0693 after correction. The Ratio of minimum to maximum transmission is 0.8104. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    0.920
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             442
_exptl_crystal_preparation       ?
_exptl_crystal_size_max          0.151
_exptl_crystal_size_mid          0.129
_exptl_crystal_size_min          0.073
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0840
_diffrn_reflns_av_unetI/netI     0.0429
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            4242
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        18.894
_diffrn_reflns_theta_max         18.894
_diffrn_reflns_theta_min         1.676
_diffrn_ambient_temperature      250.01
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                370
_reflns_number_total             469
_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 V8.38A (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_refine_diff_density_max         0.914
_refine_diff_density_min         -0.663
_refine_diff_density_rms         0.139
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.902
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     47
_refine_ls_number_reflns         469
_refine_ls_number_restraints     18
_refine_ls_R_factor_all          0.1681
_refine_ls_R_factor_gt           0.1530
_refine_ls_restrained_S_all      1.878
_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)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4108
_refine_ls_wR_factor_ref         0.4251
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C3
 1.49 with sigma of 0.01
 N1-C3 \\sim N1-C4
 with sigma of 0.01
 C3-C4_$1 \\sim C4_$1-C4
 with sigma of 0.01
3. Rigid bond restraints
 N1, C3, N1, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C3 \\sim N1 \\sim C4: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
5. Others
 Fixed Sof: C3(0.16667) H3C(0.16667) H3B(0.16667) H3A(0.16667) C4(0.5)
 H4A(0.5) H4B(0.5) H4C(0.5)
6.a Me refined with riding coordinates:
 C3(H3C,H3B,H3A), C4(H4A,H4B,H4C)
;
_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
Mn1 Mn 0.666667 0.333333 0.000000 0.082(3) Uani 1 6 d S T P . .
Cl1 Cl 0.3991(7) 0.3991(7) -0.3014(8) 0.147(4) Uani 1 2 d S T P . .
O1 O 0.5534(11) 0.3626(12) -0.1224(12) 0.114(5) Uani 1 1 d . . . . .
C1 C 0.5213(15) 0.4252(15) -0.064(2) 0.089(6) Uani 1 1 d . . . . .
C2 C 0.4595(17) 0.4595(17) -0.129(2) 0.081(7) Uani 1 2 d S T P . .
N1 N 0.666667 0.333333 0.500000 0.130(12) Uani 1 6 d DS TU P . .
C3 C 0.666667 0.333333 0.6595(11) 0.13(2) Uani 0.5 3 d DS TU P B .
H3C H 0.662686 0.396434 0.694275 0.199 Uiso 0.1667 1 calc R . . A -1
H3B H 0.603566 0.266252 0.694275 0.199 Uiso 0.1667 1 calc R . . A -1
H3A H 0.733748 0.337314 0.694275 0.199 Uiso 0.1667 1 calc R . . A -1
C4 C 0.673(4) 0.237(2) 0.4462(14) 0.22(3) Uani 0.5 1 d D U . B -1
H4A H 0.675423 0.194503 0.527049 0.325 Uiso 0.5 1 calc R . . B -1
H4B H 0.608323 0.190849 0.388204 0.325 Uiso 0.5 1 calc R . . B -1
H4C H 0.738505 0.261910 0.388206 0.325 Uiso 0.5 1 calc R . . B -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
Mn1 O1 2.155(12) 5_655 ?
Mn1 O1 2.155(12) 4_665 ?
Mn1 O1 2.155(12) 3_665 ?
Mn1 O1 2.155(12) 2_655 ?
Mn1 O1 2.155(12) . ?
Mn1 O1 2.155(12) 6 ?
Cl1 C2 1.81(2) . ?
O1 C1 1.288(17) . ?
C1 C1 1.41(3) 4_665 ?
C1 C2 1.33(2) . ?
N1 C3 1.484(10) . ?
N1 C3 1.484(10) 4_666 ?
N1 C4 1.486(14) . ?
N1 C4 1.486(14) 3_665 ?

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
O1 Mn1 O1 100.6(7) 5_655 2_655 ?
O1 Mn1 O1 94.7(5) 6 4_665 ?
O1 Mn1 O1 100.6(7) 6 . ?
O1 Mn1 O1 94.7(5) 5_655 6 ?
O1 Mn1 O1 161.0(7) 5_655 . ?
O1 Mn1 O1 73.0(7) 2_655 6 ?
O1 Mn1 O1 161.0(7) 2_655 4_665 ?
O1 Mn1 O1 73.0(7) 5_655 3_665 ?
O1 Mn1 O1 100.6(7) 3_665 4_665 ?
O1 Mn1 O1 94.7(5) 2_655 3_665 ?
O1 Mn1 O1 94.7(5) 2_655 . ?
O1 Mn1 O1 161.0(7) 6 3_665 ?
O1 Mn1 O1 73.0(7) 4_665 . ?
O1 Mn1 O1 94.7(5) 5_655 4_665 ?
O1 Mn1 O1 94.7(5) 3_665 . ?
C1 O1 Mn1 116.8(11) . . ?
O1 C1 C1 116.3(9) . 4_665 ?
O1 C1 C2 124.9(17) . . ?
C2 C1 C1 117.4(12) . 4_665 ?
C1 C2 Cl1 117.9(12) 10 . ?
C1 C2 Cl1 117.9(12) . . ?
C1 C2 C1 123(2) 10 . ?
C3 N1 C3 180.0 4_666 . ?
C3 N1 C4 70.3(4) 4_666 3_665 ?
C3 N1 C4 70.3(4) 4_666 . ?
C3 N1 C4 109.7(4) . 3_665 ?
C3 N1 C4 109.7(4) . . ?
C4 N1 C4 109.3(4) . 3_665 ?

_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 0.000 0.000 -0.647 847.3 158.7 ?

_olex2_submission_special_instructions 'No special instructions were received'

# start Validation Reply Form
_vrf_THETM01_3                   
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: The crystal diffracted to 1.1 A and data collected to 1.1 A
;
####################################################################### 
# 
# 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_4
_database_code_depnum_ccdc_archive 'CCDC 1894230'
loop_
_audit_author_name
_audit_author_address
'Lujia Liu'
;Northwestern University
United States of America
;
_audit_update_record             
;
2019-01-28 deposited with the CCDC.	2019-03-14 downloaded from the CCDC.
;
_audit_creation_date             2018-08-24
_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         'C18 Cl6 Mn2 O12, 2(C4 H12 N1)'
_chemical_formula_sum            'C26 H24 Cl6 Mn2 N2 O12'
_chemical_formula_weight         879.05
_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'
Cl Cl 0.1484 0.1585 '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'

_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      trigonal
_space_group_IT_number           162
_space_group_name_H-M_alt        'P -3 1 m'
_space_group_name_Hall           '-P 3 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-y, -x, -z'
'-x+y, y, -z'
'x, x-y, -z'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'y, x, z'
'x-y, -y, z'
'-x, -x+y, z'

_cell_length_a                   14.0339(11)
_cell_length_b                   14.0339(11)
_cell_length_c                   10.0156(8)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1708.3(3)
_cell_formula_units_Z            1
_cell_measurement_reflns_used    9917
_cell_measurement_temperature    250(2)
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.64
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.635
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.4837
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1486 before and 0.1062 after correction. The Ratio of minimum to maximum transmission is 0.6489. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            brown
_exptl_crystal_colour_modifier   ?
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    0.854
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             442
_exptl_crystal_size_max          0.223
_exptl_crystal_size_mid          0.186
_exptl_crystal_size_min          0.057
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0882
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            24027
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.419
_diffrn_reflns_theta_min         1.676
_diffrn_ambient_temperature      250.03
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                958
_reflns_number_total             1278
_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 V8.38A (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.644
_refine_diff_density_min         -0.532
_refine_diff_density_rms         0.087
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.126
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     47
_refine_ls_number_reflns         1278
_refine_ls_number_restraints     15
_refine_ls_R_factor_all          0.0863
_refine_ls_R_factor_gt           0.0750
_refine_ls_restrained_S_all      1.149
_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)+(0.1698P)²+0.7136P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2573
_refine_ls_wR_factor_ref         0.2731
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C3
 1.49 with sigma of 0.01
 N1-C4 \\sim N1-C3
 with sigma of 0.01
 C3-C4 \\sim C4-C4_$1
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C4 \\sim N1 \\sim C3: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
4. Others
 Fixed Sof: C3(0.16667) H3A(0.16667) H3B(0.16667) H3C(0.16667) C4(0.5)
 H4A(0.5) H4B(0.5) H4C(0.5)
5.a Me refined with riding coordinates:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C)
;
_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
Mn1 Mn 0.666667 0.333333 0.500000 0.0603(6) Uani 1 6 d S T P . .
Cl1 Cl 1.000000 0.39440(17) 0.78015(16) 0.0982(8) Uani 1 2 d S T P . .
O1 O 0.8077(2) 0.3605(2) 0.6156(3) 0.0679(8) Uani 1 1 d . . . . .
C1 C 0.9003(3) 0.4244(3) 0.5678(3) 0.0562(9) Uani 1 1 d . . . . .
C2 C 1.000000 0.4518(4) 0.6283(5) 0.0618(13) Uani 1 2 d S T P . .
N1 N 0.666667 0.333333 1.000000 0.170(7) Uani 1 6 d DS TU P . .
C3 C 0.666667 0.333333 1.1485(9) 0.184(8) Uani 0.5 3 d DS TU P B .
H3A H 0.600546 0.269167 1.180832 0.275 Uiso 0.1667 1 calc R . . A -1
H3B H 0.730833 0.331378 1.180833 0.275 Uiso 0.1667 1 calc R . . A -1
H3C H 0.668622 0.399454 1.180833 0.275 Uiso 0.1667 1 calc R . . A -1
C4 C 0.7697(12) 0.4334(13) 0.9417(10) 0.185(8) Uani 0.5 1 d D U . B -1
H4A H 0.766311 0.430031 0.844963 0.278 Uiso 0.5 1 calc R . . B -1
H4B H 0.772799 0.500552 0.971708 0.278 Uiso 0.5 1 calc R . . B -1
H4C H 0.835010 0.432475 0.971708 0.278 Uiso 0.5 1 calc R . . B -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
Mn1 O1 2.155(3) . ?
Mn1 O1 2.155(3) 2_655 ?
Mn1 O1 2.155(3) 3_665 ?
Mn1 O1 2.155(3) 4_666 ?
Mn1 O1 2.155(3) 5_656 ?
Mn1 O1 2.155(3) 6_556 ?
Cl1 C2 1.721(5) . ?
O1 C1 1.248(4) . ?
C1 C1 1.539(6) 6_556 ?
C1 C2 1.390(4) . ?
N1 C3 1.488(9) 4_667 ?
N1 C3 1.488(9) . ?
N1 C4 1.541(11) . ?
N1 C4 1.541(11) 2_655 ?

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
O1 Mn1 O1 100.16(17) . 4_666 ?
O1 Mn1 O1 100.16(17) 6_556 2_655 ?
O1 Mn1 O1 93.86(9) 6_556 5_656 ?
O1 Mn1 O1 74.68(13) . 6_556 ?
O1 Mn1 O1 162.36(16) . 5_656 ?
O1 Mn1 O1 93.86(10) 4_666 6_556 ?
O1 Mn1 O1 162.36(16) 4_666 2_655 ?
O1 Mn1 O1 93.86(10) . 3_665 ?
O1 Mn1 O1 93.86(10) 3_665 2_655 ?
O1 Mn1 O1 74.68(13) 4_666 3_665 ?
O1 Mn1 O1 93.86(10) 4_666 5_656 ?
O1 Mn1 O1 162.36(16) 6_556 3_665 ?
O1 Mn1 O1 74.68(13) 2_655 5_656 ?
O1 Mn1 O1 93.86(9) . 2_655 ?
O1 Mn1 O1 100.16(17) 3_665 5_656 ?
C1 O1 Mn1 117.1(2) . . ?
O1 C1 C1 115.52(19) . 6_556 ?
O1 C1 C2 125.1(3) . . ?
C2 C1 C1 119.4(2) . 6_556 ?
C1 C2 Cl1 119.4(2) . . ?
C1 C2 Cl1 119.4(2) 12_765 . ?
C1 C2 C1 121.2(4) . 12_765 ?
C3 N1 C3 180.0 . 4_667 ?
C3 N1 C4 112.3(3) . 2_655 ?
C3 N1 C4 112.3(3) . . ?
C3 N1 C4 67.7(3) 4_667 2_655 ?
C3 N1 C4 67.7(3) 4_667 . ?
C4 N1 C4 106.5(4) . 2_655 ?

_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 0.000 0.000 -0.490 947.3 219.9 ?

_olex2_submission_special_instructions 'No special instructions were received'
