# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_Complex_3
_database_code_depnum_ccdc_archive 'CCDC 1934498'
loop_
_audit_author_name
_audit_author_address
'Ennio Zangrando'
;TRIESTE Italy
Italy
;
_audit_update_record             
;
2020-03-18 deposited with the CCDC.	2020-04-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H20 Mn N2 O4, N O3'
_chemical_formula_sum            'C12 H20 Mn N3 O7'
_chemical_formula_weight         373.25

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'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

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

_cell_length_a                   18.4749(4)
_cell_length_b                   8.1865(2)
_cell_length_c                   21.1388(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3197.13(13)
_cell_formula_units_Z            8
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    4824
_cell_measurement_theta_min      2.94
_cell_measurement_theta_max      24.83

_exptl_crystal_description       Block
_exptl_crystal_colour            Black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.551
_exptl_crystal_F_000             1552
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.22
_exptl_absorpt_coefficient_mu    0.865
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.778
_exptl_absorpt_correction_T_max  0.804
_exptl_absorpt_process_details   'BRUKER SADABS'

_exptl_absorpt_special_details   ?

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            47116
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         2.887
_diffrn_reflns_theta_max         26.026
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3132
_reflns_number_gt                2538
_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.
 
 _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 SMART'
_computing_cell_refinement       'BRUKER SMART'
_computing_data_reduction        'BRUKER SAINT'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    
'Diamond. Ver. 3.2k. (Putz & Brandernburg, 2014)'
_computing_publication_material  'WinGX publication routines (Farrugia, 2012)'


_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)+(0.0413P)²+5.0381P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3132
_refine_ls_number_parameters     221
_refine_ls_number_restraints     16
_refine_ls_R_factor_all          0.0560
_refine_ls_R_factor_gt           0.0435
_refine_ls_wR_factor_ref         0.1093
_refine_ls_wR_factor_gt          0.1015
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_restrained_S_all      2.177
_refine_ls_shift/su_max          0.001
_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 0.57662(2) 0.68810(5) 0.29381(2) 0.03227(14) Uani 1 1 d . . . . .
N1 N 0.68444(12) 0.6890(3) 0.30609(11) 0.0372(5) Uani 1 1 d . . . . .
N2 N 0.55715(13) 0.6625(3) 0.38786(11) 0.0391(5) Uani 1 1 d . . . . .
H2A H 0.556276 0.544299 0.395117 0.047 Uiso 1 1 calc DR U . . .
O1 O 0.58841(10) 0.6987(2) 0.20613(9) 0.0411(5) Uani 1 1 d . . . . .
O2 O 0.47503(10) 0.6796(2) 0.28697(9) 0.0400(5) Uani 1 1 d D . . . .
O4 O 0.57932(14) 0.9636(3) 0.30130(11) 0.0509(6) Uani 1 1 d D . . . .
H4A H 0.560(2) 1.024(4) 0.2739(13) 0.076 Uiso 1 1 d D U . . .
H4B H 0.583(2) 1.017(4) 0.3345(11) 0.076 Uiso 1 1 d D U . . .
O3 O 0.58404(13) 0.4080(2) 0.29059(10) 0.0472(5) Uani 1 1 d D . . . .
H3A H 0.566(2) 0.349(4) 0.2612(11) 0.071 Uiso 1 1 d D U . . .
H3B H 0.582(2) 0.353(4) 0.3232(10) 0.071 Uiso 1 1 d D U . . .
C1 C 0.63914(15) 0.6186(3) 0.17439(13) 0.0374(6) Uani 1 1 d . . . . .
C2 C 0.62774(18) 0.5807(4) 0.11072(14) 0.0467(7) Uani 1 1 d . . . . .
H2 H 0.584897 0.612758 0.091238 0.056 Uiso 1 1 calc R U . . .
C3 C 0.6788(2) 0.4969(4) 0.07644(16) 0.0591(9) Uani 1 1 d . . . . .
H3 H 0.669906 0.471628 0.034264 0.071 Uiso 1 1 calc R U . . .
C4 C 0.7439(2) 0.4494(4) 0.10420(18) 0.0647(10) Uani 1 1 d . . . . .
H4 H 0.777807 0.390666 0.081009 0.078 Uiso 1 1 calc R U . . .
C5 C 0.75739(18) 0.4897(4) 0.16550(17) 0.0527(8) Uani 1 1 d . . . . .
H5 H 0.801362 0.460358 0.183643 0.063 Uiso 1 1 calc R U . . .
C6 C 0.70625(15) 0.5747(3) 0.20186(14) 0.0398(6) Uani 1 1 d . . . . .
C7 C 0.72654(15) 0.6284(4) 0.26387(15) 0.0419(7) Uani 1 1 d . . . . .
H7 H 0.775146 0.618312 0.274628 0.050 Uiso 1 1 calc R U . . .
C8 C 0.71639(17) 0.7576(4) 0.36422(15) 0.0510(8) Uani 1 1 d . . . . .
H8A H 0.707980 0.874580 0.364890 0.061 Uiso 1 1 calc R U . . .
H8B H 0.768302 0.740080 0.363403 0.061 Uiso 1 1 calc R U . . .
C9 C 0.68589(19) 0.6836(4) 0.42399(15) 0.0537(8) Uani 1 1 d . . . . .
H9A H 0.689492 0.565602 0.421065 0.064 Uiso 1 1 calc R U . . .
H9B H 0.715323 0.718324 0.459520 0.064 Uiso 1 1 calc R U . . .
C10 C 0.60819(19) 0.7287(4) 0.43698(15) 0.0502(8) Uani 1 1 d . . . . .
H10A H 0.594386 0.686684 0.478156 0.060 Uiso 1 1 calc R U . . .
H10B H 0.603899 0.846726 0.438274 0.060 Uiso 1 1 calc R U . . .
C11 C 0.48219(18) 0.7166(4) 0.39844(15) 0.0532(8) Uani 1 1 d . . . . .
H11A H 0.479504 0.834974 0.398725 0.064 Uiso 1 1 calc R U . . .
H11B H 0.464337 0.675981 0.438620 0.064 Uiso 1 1 calc R U . . .
C12 C 0.43835(17) 0.6481(4) 0.34477(16) 0.0519(8) Uani 1 1 d . . . . .
H12A H 0.432062 0.531397 0.350358 0.062 Uiso 1 1 calc R U . . .
H12B H 0.390870 0.698696 0.344034 0.062 Uiso 1 1 calc R U . . .
N3 N 0.5665(5) 1.2149(8) 0.4343(4) 0.0760(12) Uani 0.514(5) 1 d D . P . .
O10 O 0.6068(4) 1.2006(6) 0.3891(3) 0.0760(12) Uani 0.514(5) 1 d D . P A .
O11 O 0.5354(4) 1.3530(6) 0.4439(3) 0.0760(12) Uani 0.514(5) 1 d D . P A .
O12 O 0.5404(3) 1.1009(6) 0.4630(2) 0.0760(12) Uani 0.514(5) 1 d D . P A .
N4 N 0.6000(5) 1.2456(11) 0.4344(4) 0.0819(13) Uani 0.486(5) 1 d D . P A 2
O20 O 0.6217(4) 1.1157(8) 0.4148(3) 0.0819(13) Uani 0.486(5) 1 d D . P A 2
O21 O 0.6319(4) 1.3245(7) 0.4728(3) 0.0819(13) Uani 0.486(5) 1 d D . P A 2
O22 O 0.5414(4) 1.2946(9) 0.4150(4) 0.0819(13) Uani 0.486(5) 1 d D . P 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 O1 1.8682(19) . ?
Mn1 O2 1.8837(19) . ?
Mn1 N1 2.009(2) . ?
Mn1 N2 2.031(2) . ?
Mn1 O4 2.261(2) . ?
Mn1 O3 2.298(2) . ?
N1 C7 1.283(4) . ?
N1 C8 1.475(4) . ?
N2 C11 1.471(4) . ?
N2 C10 1.504(4) . ?
N2 H2A 0.9800 . ?
O1 C1 1.326(3) . ?
O2 C12 1.421(4) . ?
O4 H4A 0.839(18) . ?
O4 H4B 0.832(18) . ?
O3 H3A 0.852(18) . ?
O3 H3B 0.825(18) . ?
C1 C2 1.397(4) . ?
C1 C6 1.415(4) . ?
C2 C3 1.374(5) . ?
C2 H2 0.9300 . ?
C3 C4 1.393(5) . ?
C3 H3 0.9300 . ?
C4 C5 1.360(5) . ?
C4 H4 0.9300 . ?
C5 C6 1.403(4) . ?
C5 H5 0.9300 . ?
C6 C7 1.432(4) . ?
C7 H7 0.9300 . ?
C8 C9 1.510(5) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C9 C10 1.507(5) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C10 H10A 0.9700 . ?
C10 H10B 0.9700 . ?
C11 C12 1.503(5) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
N3 O12 1.214(8) . ?
N3 O10 1.216(8) . ?
N3 O11 1.285(8) . ?
N4 O21 1.193(9) . ?
N4 O20 1.209(9) . ?
N4 O22 1.225(10) . ?

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 O2 92.39(9) . . ?
O1 Mn1 N1 90.71(9) . . ?
O2 Mn1 N1 176.43(9) . . ?
O1 Mn1 N2 175.18(10) . . ?
O2 Mn1 N2 83.97(9) . . ?
N1 Mn1 N2 92.84(10) . . ?
O1 Mn1 O4 91.19(9) . . ?
O2 Mn1 O4 93.69(9) . . ?
N1 Mn1 O4 88.03(9) . . ?
N2 Mn1 O4 92.19(9) . . ?
O1 Mn1 O3 90.56(9) . . ?
O2 Mn1 O3 91.16(8) . . ?
N1 Mn1 O3 87.03(9) . . ?
N2 Mn1 O3 86.37(9) . . ?
O4 Mn1 O3 174.78(8) . . ?
C7 N1 C8 119.0(2) . . ?
C7 N1 Mn1 120.6(2) . . ?
C8 N1 Mn1 120.4(2) . . ?
C11 N2 C10 112.1(2) . . ?
C11 N2 Mn1 106.53(18) . . ?
C10 N2 Mn1 121.9(2) . . ?
C11 N2 H2A 105.0 . . ?
C10 N2 H2A 105.0 . . ?
Mn1 N2 H2A 105.0 . . ?
C1 O1 Mn1 124.17(17) . . ?
C12 O2 Mn1 114.58(18) . . ?
Mn1 O4 H4A 122(3) . . ?
Mn1 O4 H4B 126(3) . . ?
H4A O4 H4B 108(3) . . ?
Mn1 O3 H3A 124(2) . . ?
Mn1 O3 H3B 121(3) . . ?
H3A O3 H3B 106(3) . . ?
O1 C1 C2 119.4(3) . . ?
O1 C1 C6 122.5(3) . . ?
C2 C1 C6 118.1(3) . . ?
C3 C2 C1 121.0(3) . . ?
C3 C2 H2 119.5 . . ?
C1 C2 H2 119.5 . . ?
C2 C3 C4 120.7(3) . . ?
C2 C3 H3 119.7 . . ?
C4 C3 H3 119.7 . . ?
C5 C4 C3 119.5(3) . . ?
C5 C4 H4 120.3 . . ?
C3 C4 H4 120.3 . . ?
C4 C5 C6 121.2(3) . . ?
C4 C5 H5 119.4 . . ?
C6 C5 H5 119.4 . . ?
C5 C6 C1 119.4(3) . . ?
C5 C6 C7 118.5(3) . . ?
C1 C6 C7 121.8(3) . . ?
N1 C7 C6 126.6(3) . . ?
N1 C7 H7 116.7 . . ?
C6 C7 H7 116.7 . . ?
N1 C8 C9 113.2(3) . . ?
N1 C8 H8A 108.9 . . ?
C9 C8 H8A 108.9 . . ?
N1 C8 H8B 108.9 . . ?
C9 C8 H8B 108.9 . . ?
H8A C8 H8B 107.7 . . ?
C10 C9 C8 114.2(3) . . ?
C10 C9 H9A 108.7 . . ?
C8 C9 H9A 108.7 . . ?
C10 C9 H9B 108.7 . . ?
C8 C9 H9B 108.7 . . ?
H9A C9 H9B 107.6 . . ?
N2 C10 C9 112.5(3) . . ?
N2 C10 H10A 109.1 . . ?
C9 C10 H10A 109.1 . . ?
N2 C10 H10B 109.1 . . ?
C9 C10 H10B 109.1 . . ?
H10A C10 H10B 107.8 . . ?
N2 C11 C12 106.3(2) . . ?
N2 C11 H11A 110.5 . . ?
C12 C11 H11A 110.5 . . ?
N2 C11 H11B 110.5 . . ?
C12 C11 H11B 110.5 . . ?
H11A C11 H11B 108.7 . . ?
O2 C12 C11 108.9(3) . . ?
O2 C12 H12A 109.9 . . ?
C11 C12 H12A 109.9 . . ?
O2 C12 H12B 109.9 . . ?
C11 C12 H12B 109.9 . . ?
H12A C12 H12B 108.3 . . ?
O12 N3 O10 124.3(7) . . ?
O12 N3 O11 114.7(7) . . ?
O10 N3 O11 118.9(7) . . ?
O21 N4 O20 123.0(9) . . ?
O21 N4 O22 119.1(9) . . ?
O20 N4 O22 117.8(9) . . ?

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
_geom_hbond_publ_flag
N2 H2A O11 0.98 1.91 2.826(5) 153.6 1_545 yes
O4 H4A O2 0.839(18) 1.925(19) 2.760(3) 173(4) 4_655 yes
O4 H4B N3 0.832(18) 2.67(2) 3.491(8) 168(3) . yes
O4 H4B O10 0.832(18) 1.94(2) 2.733(6) 158(4) . yes
O3 H3A O2 0.852(18) 1.88(2) 2.716(3) 165(3) 4_645 yes
O3 H3B N3 0.825(18) 2.621(19) 3.440(8) 172(3) 1_545 yes
O3 H3B O10 0.825(18) 1.93(2) 2.720(6) 161(4) 1_545 yes
C2 H2 O12 0.93 2.58 3.479(7) 161.4 4_645 yes
C8 H8B O10 0.97 2.39 3.341(7) 165.8 7_755 yes
C10 H10B O12 0.97 2.45 3.341(6) 153.2 . yes
C11 H11B O11 0.97 2.49 3.396(6) 154.6 5_676 yes

_refine_diff_density_max         0.668
_refine_diff_density_min         -0.490
_refine_diff_density_rms         0.057

####################################################################### 
# 
# 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_Complex_4
_database_code_depnum_ccdc_archive 'CCDC 1934499'
loop_
_audit_author_name
_audit_author_address
'Ennio Zangrando'
;TRIESTE Italy
Italy
;
_audit_update_record             
;
2020-03-18 deposited with the CCDC.	2020-04-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C39 H48 Mn3 N9 O6 S3, 0.5(H2 O) 0.25(O)'
_chemical_formula_sum            'C39 H49 Mn3 N9 O6.75 S3'
_chemical_formula_weight         1012.87

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'
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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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'

_cell_length_a                   14.004(2)
_cell_length_b                   14.366(2)
_cell_length_c                   14.520(3)
_cell_angle_alpha                67.61(3)
_cell_angle_beta                 61.177(17)
_cell_angle_gamma                78.511(19)
_cell_volume                     2365.9(9)
_cell_formula_units_Z            2
_cell_measurement_temperature    295(2)
_cell_measurement_reflns_used    4824
_cell_measurement_theta_min      2.24
_cell_measurement_theta_max      19.83

_exptl_crystal_description       plate
_exptl_crystal_colour            black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_F_000             1046
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.18
_exptl_absorpt_coefficient_mu    0.975
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.611
_exptl_absorpt_correction_T_max  0.705
_exptl_absorpt_process_details   'BRUKER SADABS'

_exptl_absorpt_special_details   ?

_diffrn_ambient_temperature      295(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            37281
_diffrn_reflns_av_unetI/netI     0.2404
_diffrn_reflns_av_R_equivalents  0.1670
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.238
_diffrn_reflns_theta_max         25.046
_diffrn_reflns_theta_full        25.046
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measured_fraction_theta_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_point_group_measured_fraction_full 0.986
_reflns_number_total             8261
_reflns_number_gt                3159
_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.
 
 _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 SMART'
_computing_cell_refinement       'BRUKER SMART'
_computing_data_reduction        'BRUKER SAINT'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    
'Diamond. Ver. 3.2k. (Putz & Brandernburg, 2014)'
_computing_publication_material  'WinGX publication routines (Farrugia, 2012)'


_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)+(0.1263P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         8261
_refine_ls_number_parameters     554
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.2359
_refine_ls_R_factor_gt           0.0987
_refine_ls_wR_factor_ref         0.2776
_refine_ls_wR_factor_gt          0.2290
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_restrained_S_all      0.985
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.001

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 0.67519(13) 0.78007(11) 0.85229(13) 0.0529(5) Uani 1 1 d . . . . .
N1 N 0.7430(7) 0.8849(6) 0.7014(7) 0.051(2) Uani 1 1 d . . . . .
N2 N 0.8050(7) 0.6855(6) 0.8103(6) 0.051(2) Uani 1 1 d . . . . .
H2A H 0.793167 0.653883 0.767631 0.061 Uiso 1 1 calc R U . . .
O1 O 0.5387(5) 0.8463(4) 0.8807(5) 0.0467(17) Uani 1 1 d . . . . .
O2 O 0.6152(5) 0.6751(5) 0.9893(5) 0.0479(18) Uani 1 1 d . . . . .
C1 C 0.5017(9) 0.8999(7) 0.8067(9) 0.042(3) Uani 1 1 d . . . . .
C2 C 0.3907(9) 0.9112(7) 0.8423(9) 0.054(3) Uani 1 1 d . . . . .
H2 H 0.342219 0.881149 0.916506 0.065 Uiso 1 1 calc R U . . .
C3 C 0.3532(9) 0.9686(8) 0.7647(12) 0.071(4) Uani 1 1 d . . . . .
H3 H 0.278204 0.974900 0.789198 0.086 Uiso 1 1 calc R U . . .
C4 C 0.4191(11) 1.0172(8) 0.6534(10) 0.071(4) Uani 1 1 d . . . . .
H4 H 0.391085 1.055996 0.603733 0.086 Uiso 1 1 calc R U . . .
C5 C 0.5309(10) 1.0038(7) 0.6212(9) 0.059(3) Uani 1 1 d . . . . .
H5 H 0.578473 1.035175 0.547062 0.071 Uiso 1 1 calc R U . . .
C6 C 0.5753(9) 0.9461(7) 0.6936(9) 0.045(3) Uani 1 1 d . . . . .
C7 C 0.6901(9) 0.9415(8) 0.6509(9) 0.055(3) Uani 1 1 d . . . . .
H7 H 0.729923 0.984223 0.579008 0.066 Uiso 1 1 calc R U . . .
C8 C 0.8610(10) 0.8970(8) 0.6442(10) 0.074(4) Uani 1 1 d . . . . .
H8A H 0.881028 0.923380 0.684744 0.089 Uiso 1 1 calc R U . . .
H8B H 0.880587 0.946539 0.570532 0.089 Uiso 1 1 calc R U . . .
C9 C 0.9261(9) 0.8023(9) 0.6323(9) 0.071(3) Uani 1 1 d . . . . .
H9A H 1.002425 0.819177 0.585269 0.085 Uiso 1 1 calc R U . . .
H9B H 0.903763 0.774169 0.594722 0.085 Uiso 1 1 calc R U . . .
C10 C 0.9145(9) 0.7234(9) 0.7407(9) 0.072(3) Uani 1 1 d . . . . .
H10A H 0.964995 0.667951 0.725539 0.086 Uiso 1 1 calc R U . . .
H10B H 0.933572 0.751845 0.780315 0.086 Uiso 1 1 calc R U . . .
C11 C 0.7915(9) 0.6033(8) 0.9154(8) 0.059(3) Uani 1 1 d . . . . .
H11A H 0.818530 0.623337 0.955210 0.071 Uiso 1 1 calc R U . . .
H11B H 0.831249 0.543166 0.900001 0.071 Uiso 1 1 calc R U . . .
C12 C 0.6726(8) 0.5842(7) 0.9822(8) 0.045(3) Uani 1 1 d . . . . .
H12A H 0.648913 0.553915 0.947361 0.055 Uiso 1 1 calc R U . . .
H12B H 0.657661 0.537675 1.056385 0.055 Uiso 1 1 calc R U . . .
Mn2 Mn 0.68341(12) 0.63305(11) 0.64288(12) 0.0464(5) Uani 1 1 d . . . . .
N3 N 0.7379(7) 0.5776(6) 0.5194(6) 0.045(2) Uani 1 1 d . . . . .
N4 N 0.5311(6) 0.6494(5) 0.6541(6) 0.0358(19) Uani 1 1 d . . . . .
H4A H 0.500969 0.581640 0.692869 0.043 Uiso 1 1 calc R U . . .
O3 O 0.8111(5) 0.5855(5) 0.6614(5) 0.0422(16) Uani 1 1 d . . . . .
O4 O 0.6200(5) 0.6748(4) 0.7682(5) 0.0424(17) Uani 1 1 d . . . . .
C21 C 0.8652(7) 0.4983(8) 0.6512(8) 0.041(3) Uani 1 1 d . . . . .
C22 C 0.9245(8) 0.4487(8) 0.7075(8) 0.050(3) Uani 1 1 d . . . . .
H22 H 0.928468 0.476490 0.753815 0.059 Uiso 1 1 calc R U . . .
C23 C 0.9786(9) 0.3601(9) 0.6993(10) 0.064(3) Uani 1 1 d . . . . .
H23 H 1.016189 0.327892 0.741449 0.077 Uiso 1 1 calc R U . . .
C24 C 0.9780(9) 0.3178(8) 0.6292(10) 0.068(4) Uani 1 1 d . . . . .
H24 H 1.015793 0.257908 0.622150 0.082 Uiso 1 1 calc R U . . .
C25 C 0.9201(8) 0.3663(8) 0.5700(9) 0.059(3) Uani 1 1 d . . . . .
H25 H 0.919514 0.338569 0.521894 0.070 Uiso 1 1 calc R U . . .
C26 C 0.8630(7) 0.4545(7) 0.5791(8) 0.042(3) Uani 1 1 d . . . . .
C27 C 0.8065(9) 0.5055(8) 0.5092(8) 0.050(3) Uani 1 1 d . . . . .
H27 H 0.822937 0.482197 0.451414 0.060 Uiso 1 1 calc R U . . .
C28 C 0.6995(8) 0.6210(8) 0.4303(8) 0.055(3) Uani 1 1 d . . . . .
H28A H 0.724929 0.689426 0.386756 0.066 Uiso 1 1 calc R U . . .
H28B H 0.730437 0.581625 0.380589 0.066 Uiso 1 1 calc R U . . .
C29 C 0.5772(9) 0.6211(8) 0.4805(8) 0.057(3) Uani 1 1 d . . . . .
H29A H 0.552858 0.552825 0.526842 0.069 Uiso 1 1 calc R U . . .
H29B H 0.556564 0.640879 0.420586 0.069 Uiso 1 1 calc R U . . .
C30 C 0.5173(8) 0.6890(7) 0.5495(8) 0.051(3) Uani 1 1 d . . . . .
H30A H 0.545647 0.756514 0.507081 0.061 Uiso 1 1 calc R U . . .
H30B H 0.440449 0.692130 0.568396 0.061 Uiso 1 1 calc R U . . .
C31 C 0.4687(8) 0.7048(7) 0.7309(9) 0.054(3) Uani 1 1 d . . . . .
H31A H 0.391451 0.692932 0.763727 0.065 Uiso 1 1 calc R U . . .
H31B H 0.480895 0.776461 0.692400 0.065 Uiso 1 1 calc R U . . .
C32 C 0.5071(8) 0.6674(6) 0.8191(7) 0.040(3) Uani 1 1 d . . . . .
H32A H 0.473603 0.707430 0.868194 0.048 Uiso 1 1 calc R U . . .
H32B H 0.486377 0.597939 0.863259 0.048 Uiso 1 1 calc R U . . .
Mn3 Mn 0.52269(12) 0.35406(10) 0.78052(13) 0.0469(5) Uani 1 1 d . . . . .
N5 N 0.4342(8) 0.2442(6) 0.8045(6) 0.046(2) Uani 1 1 d . . . . .
N6 N 0.5958(7) 0.2525(6) 0.8691(6) 0.049(2) Uani 1 1 d . . . . .
H6A H 0.541492 0.234161 0.947531 0.058 Uiso 1 1 calc R U . . .
O5 O 0.4216(5) 0.4510(4) 0.7457(5) 0.0467(17) Uani 1 1 d . . . . .
O6 O 0.5950(5) 0.4514(4) 0.7786(5) 0.0419(17) Uani 1 1 d . . . . .
C41 C 0.3161(9) 0.4411(7) 0.7841(7) 0.039(2) Uani 1 1 d . . . . .
C42 C 0.2473(10) 0.5217(9) 0.7817(10) 0.067(3) Uani 1 1 d . . . . .
H42 H 0.277071 0.585437 0.747870 0.081 Uiso 1 1 calc R U . . .
C43 C 0.1379(11) 0.5158(10) 0.8252(11) 0.078(4) Uani 1 1 d . . . . .
H43 H 0.094249 0.573795 0.824567 0.094 Uiso 1 1 calc R U . . .
C44 C 0.0904(11) 0.4194(13) 0.8722(11) 0.091(4) Uani 1 1 d . . . . .
H44 H 0.015676 0.413119 0.900874 0.109 Uiso 1 1 calc R U . . .
C45 C 0.1563(11) 0.3390(10) 0.8737(9) 0.068(4) Uani 1 1 d . . . . .
H45 H 0.126700 0.275386 0.905234 0.082 Uiso 1 1 calc R U . . .
C46 C 0.2698(9) 0.3472(8) 0.8288(8) 0.048(3) Uani 1 1 d . . . . .
C47 C 0.3335(10) 0.2566(8) 0.8279(8) 0.050(3) Uani 1 1 d . . . . .
H47 H 0.297178 0.199666 0.846664 0.060 Uiso 1 1 calc R U . . .
C48 C 0.4880(10) 0.1468(8) 0.7945(8) 0.066(3) Uani 1 1 d . . . . .
H48A H 0.541839 0.157050 0.717712 0.079 Uiso 1 1 calc R U . . .
H48B H 0.434111 0.101215 0.812791 0.079 Uiso 1 1 calc R U . . .
C49 C 0.5434(10) 0.0985(8) 0.8692(9) 0.072(4) Uani 1 1 d . . . . .
H49A H 0.570515 0.032372 0.863222 0.087 Uiso 1 1 calc R U . . .
H49B H 0.488890 0.088686 0.945602 0.087 Uiso 1 1 calc R U . . .
C50 C 0.6398(9) 0.1570(8) 0.8457(9) 0.065(3) Uani 1 1 d . . . . .
H50A H 0.674070 0.116869 0.893042 0.078 Uiso 1 1 calc R U . . .
H50B H 0.694025 0.170912 0.768625 0.078 Uiso 1 1 calc R U . . .
C51 C 0.6842(8) 0.3085(7) 0.8573(8) 0.046(3) Uani 1 1 d . . . . .
H51A H 0.702665 0.275322 0.918784 0.055 Uiso 1 1 calc R U . . .
H51B H 0.749352 0.312814 0.787888 0.055 Uiso 1 1 calc R U . . .
C52 C 0.6352(8) 0.4108(7) 0.8586(7) 0.044(3) Uani 1 1 d . . . . .
H52A H 0.576300 0.406060 0.931997 0.053 Uiso 1 1 calc R U . . .
H52B H 0.689938 0.454632 0.841968 0.053 Uiso 1 1 calc R U . . .
S1 S 0.8527(4) 0.9678(3) 0.9452(4) 0.1147(15) Uani 1 1 d . . . . .
N7 N 0.7426(8) 0.8588(7) 0.9094(8) 0.064(3) Uani 1 1 d . . . . .
C17 C 0.7891(9) 0.9039(8) 0.9203(9) 0.057(3) Uani 1 1 d . . . . .
S2 S 0.8602(3) 0.9458(3) 0.3607(3) 0.1060(14) Uani 1 1 d . . . . .
N8 N 0.7337(7) 0.7791(7) 0.5226(7) 0.063(3) Uani 1 1 d . . . . .
C18 C 0.7860(9) 0.8476(9) 0.4535(10) 0.067(4) Uani 1 1 d . . . . .
S3 S 0.7634(3) 0.2435(3) 0.4676(3) 0.0898(12) Uani 1 1 d . . . . .
N9 N 0.6331(8) 0.3412(6) 0.6201(7) 0.057(3) Uani 1 1 d . . . . .
C19 C 0.6880(9) 0.3010(8) 0.5553(9) 0.051(3) Uani 1 1 d . . . . .
O1W O 0.8241(13) 0.2919(14) 1.0486(16) 0.131(7) Uani 0.5 1 d . U P . .
H11 H 0.846643 0.345195 0.995394 0.197 Uiso 0.5 1 d R U P . .
H12 H 0.863293 0.288993 1.088636 0.197 Uiso 0.5 1 d R U P . .
O2W O 0.879(3) 0.199(2) 1.156(3) 0.095(11) Uiso 0.25 1 d . . 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 O2 1.883(6) . ?
Mn1 O1 1.883(6) . ?
Mn1 N1 2.005(9) . ?
Mn1 N2 2.024(8) . ?
Mn1 N7 2.180(11) . ?
Mn1 O4 2.675(6) . ?
N1 C7 1.256(12) . ?
N1 C8 1.459(13) . ?
N2 C10 1.445(12) . ?
N2 C11 1.483(11) . ?
N2 H2A 0.9800 . ?
O1 C1 1.328(11) . ?
O2 C12 1.402(10) . ?
C1 C2 1.379(13) . ?
C1 C6 1.417(13) . ?
C2 C3 1.384(14) . ?
C2 H2 0.9300 . ?
C3 C4 1.381(15) . ?
C3 H3 0.9300 . ?
C4 C5 1.396(14) . ?
C4 H4 0.9300 . ?
C5 C6 1.393(13) . ?
C5 H5 0.9300 . ?
C6 C7 1.415(14) . ?
C7 H7 0.9300 . ?
C8 C9 1.499(13) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C9 C10 1.502(14) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C10 H10A 0.9700 . ?
C10 H10B 0.9700 . ?
C11 C12 1.488(13) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
Mn2 O4 1.876(6) . ?
Mn2 O3 1.890(6) . ?
Mn2 N3 1.990(8) . ?
Mn2 N4 2.031(7) . ?
Mn2 N8 2.135(9) . ?
Mn2 O6 2.692(6) . ?
N3 C27 1.265(11) . ?
N3 C28 1.509(11) . ?
N4 C31 1.449(11) . ?
N4 C30 1.499(10) . ?
N4 H4A 0.9800 . ?
O3 C21 1.349(10) . ?
O4 C32 1.392(10) . ?
C21 C22 1.356(12) . ?
C21 C26 1.427(13) . ?
C22 C23 1.361(13) . ?
C22 H22 0.9300 . ?
C23 C24 1.373(15) . ?
C23 H23 0.9300 . ?
C24 C25 1.367(14) . ?
C24 H24 0.9300 . ?
C25 C26 1.373(12) . ?
C25 H25 0.9300 . ?
C26 C27 1.473(13) . ?
C27 H27 0.9300 . ?
C28 C29 1.504(13) . ?
C28 H28A 0.9700 . ?
C28 H28B 0.9700 . ?
C29 C30 1.506(13) . ?
C29 H29A 0.9700 . ?
C29 H29B 0.9700 . ?
C30 H30A 0.9700 . ?
C30 H30B 0.9700 . ?
C31 C32 1.498(13) . ?
C31 H31A 0.9700 . ?
C31 H31B 0.9700 . ?
C32 H32A 0.9700 . ?
C32 H32B 0.9700 . ?
Mn3 O6 1.867(6) . ?
Mn3 O5 1.889(6) . ?
Mn3 N6 2.019(7) . ?
Mn3 N5 2.023(8) . ?
Mn3 N9 2.143(9) . ?
N5 C47 1.272(11) . ?
N5 C48 1.476(11) . ?
N6 C50 1.481(11) . ?
N6 C51 1.516(12) . ?
N6 H6A 0.9800 . ?
O5 C41 1.320(11) . ?
O6 C52 1.411(10) . ?
C41 C42 1.353(13) . ?
C41 C46 1.391(13) . ?
C42 C43 1.353(14) . ?
C42 H42 0.9300 . ?
C43 C44 1.427(17) . ?
C43 H43 0.9300 . ?
C44 C45 1.328(15) . ?
C44 H44 0.9300 . ?
C45 C46 1.408(14) . ?
C45 H45 0.9300 . ?
C46 C47 1.425(14) . ?
C47 H47 0.9300 . ?
C48 C49 1.511(14) . ?
C48 H48A 0.9700 . ?
C48 H48B 0.9700 . ?
C49 C50 1.560(15) . ?
C49 H49A 0.9700 . ?
C49 H49B 0.9700 . ?
C50 H50A 0.9700 . ?
C50 H50B 0.9700 . ?
C51 C52 1.495(11) . ?
C51 H51A 0.9700 . ?
C51 H51B 0.9700 . ?
C52 H52A 0.9700 . ?
C52 H52B 0.9700 . ?
S1 C17 1.629(13) . ?
N7 C17 1.103(12) . ?
S2 C18 1.635(13) . ?
N8 C18 1.157(12) . ?
S3 C19 1.604(13) . ?
N9 C19 1.162(12) . ?
O1W H11 0.8328 . ?
O1W H12 0.9589 . ?
O2W H12 1.3439 . ?

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
O2 Mn1 O1 91.8(3) . . ?
O2 Mn1 N1 176.2(3) . . ?
O1 Mn1 N1 90.5(3) . . ?
O2 Mn1 N2 85.5(3) . . ?
O1 Mn1 N2 164.2(3) . . ?
N1 Mn1 N2 91.5(3) . . ?
O2 Mn1 N7 95.2(3) . . ?
O1 Mn1 N7 100.3(3) . . ?
N1 Mn1 N7 87.5(3) . . ?
N2 Mn1 N7 95.4(3) . . ?
O2 Mn1 O4 86.6(2) . . ?
O1 Mn1 O4 87.1(2) . . ?
N1 Mn1 O4 90.4(3) . . ?
N2 Mn1 O4 77.2(3) . . ?
N7 Mn1 O4 172.3(3) . . ?
C7 N1 C8 116.8(9) . . ?
C7 N1 Mn1 123.9(8) . . ?
C8 N1 Mn1 119.3(7) . . ?
C10 N2 C11 113.7(8) . . ?
C10 N2 Mn1 121.0(7) . . ?
C11 N2 Mn1 106.1(6) . . ?
C10 N2 H2A 104.8 . . ?
C11 N2 H2A 104.8 . . ?
Mn1 N2 H2A 104.8 . . ?
C1 O1 Mn1 127.0(6) . . ?
C12 O2 Mn1 111.1(5) . . ?
O1 C1 C2 118.7(9) . . ?
O1 C1 C6 120.5(9) . . ?
C2 C1 C6 120.7(10) . . ?
C1 C2 C3 118.2(11) . . ?
C1 C2 H2 120.9 . . ?
C3 C2 H2 120.9 . . ?
C4 C3 C2 124.8(11) . . ?
C4 C3 H3 117.6 . . ?
C2 C3 H3 117.6 . . ?
C3 C4 C5 115.0(11) . . ?
C3 C4 H4 122.5 . . ?
C5 C4 H4 122.5 . . ?
C6 C5 C4 123.8(11) . . ?
C6 C5 H5 118.1 . . ?
C4 C5 H5 118.1 . . ?
C5 C6 C7 118.1(10) . . ?
C5 C6 C1 117.4(10) . . ?
C7 C6 C1 124.4(10) . . ?
N1 C7 C6 125.9(10) . . ?
N1 C7 H7 117.1 . . ?
C6 C7 H7 117.1 . . ?
N1 C8 C9 114.7(9) . . ?
N1 C8 H8A 108.6 . . ?
C9 C8 H8A 108.6 . . ?
N1 C8 H8B 108.6 . . ?
C9 C8 H8B 108.6 . . ?
H8A C8 H8B 107.6 . . ?
C8 C9 C10 114.3(10) . . ?
C8 C9 H9A 108.7 . . ?
C10 C9 H9A 108.7 . . ?
C8 C9 H9B 108.7 . . ?
C10 C9 H9B 108.7 . . ?
H9A C9 H9B 107.6 . . ?
N2 C10 C9 112.0(9) . . ?
N2 C10 H10A 109.2 . . ?
C9 C10 H10A 109.2 . . ?
N2 C10 H10B 109.2 . . ?
C9 C10 H10B 109.2 . . ?
H10A C10 H10B 107.9 . . ?
N2 C11 C12 106.1(8) . . ?
N2 C11 H11A 110.5 . . ?
C12 C11 H11A 110.5 . . ?
N2 C11 H11B 110.5 . . ?
C12 C11 H11B 110.5 . . ?
H11A C11 H11B 108.7 . . ?
O2 C12 C11 109.7(8) . . ?
O2 C12 H12A 109.7 . . ?
C11 C12 H12A 109.7 . . ?
O2 C12 H12B 109.7 . . ?
C11 C12 H12B 109.7 . . ?
H12A C12 H12B 108.2 . . ?
O4 Mn2 O3 92.1(3) . . ?
O4 Mn2 N3 173.7(3) . . ?
O3 Mn2 N3 90.3(3) . . ?
O4 Mn2 N4 85.6(3) . . ?
O3 Mn2 N4 165.1(3) . . ?
N3 Mn2 N4 90.6(3) . . ?
O4 Mn2 N8 95.9(3) . . ?
O3 Mn2 N8 100.5(3) . . ?
N3 Mn2 N8 89.3(3) . . ?
N4 Mn2 N8 94.3(3) . . ?
O4 Mn2 O6 88.3(2) . . ?
O3 Mn2 O6 88.9(2) . . ?
N3 Mn2 O6 85.9(3) . . ?
N4 Mn2 O6 76.3(2) . . ?
N8 Mn2 O6 169.4(3) . . ?
C27 N3 C28 115.6(8) . . ?
C27 N3 Mn2 123.3(7) . . ?
C28 N3 Mn2 121.0(6) . . ?
C31 N4 C30 114.0(7) . . ?
C31 N4 Mn2 105.5(6) . . ?
C30 N4 Mn2 119.4(6) . . ?
C31 N4 H4A 105.6 . . ?
C30 N4 H4A 105.6 . . ?
Mn2 N4 H4A 105.6 . . ?
C21 O3 Mn2 126.1(6) . . ?
C32 O4 Mn2 110.3(5) . . ?
C32 O4 Mn1 109.6(5) . . ?
Mn2 O4 Mn1 138.3(3) . . ?
O3 C21 C22 122.3(10) . . ?
O3 C21 C26 120.8(9) . . ?
C22 C21 C26 116.9(9) . . ?
C21 C22 C23 123.1(11) . . ?
C21 C22 H22 118.5 . . ?
C23 C22 H22 118.5 . . ?
C22 C23 C24 120.5(11) . . ?
C22 C23 H23 119.8 . . ?
C24 C23 H23 119.8 . . ?
C25 C24 C23 118.1(11) . . ?
C25 C24 H24 120.9 . . ?
C23 C24 H24 120.9 . . ?
C24 C25 C26 122.2(11) . . ?
C24 C25 H25 118.9 . . ?
C26 C25 H25 118.9 . . ?
C25 C26 C21 119.1(10) . . ?
C25 C26 C27 119.6(10) . . ?
C21 C26 C27 121.2(9) . . ?
N3 C27 C26 126.9(10) . . ?
N3 C27 H27 116.6 . . ?
C26 C27 H27 116.6 . . ?
C29 C28 N3 111.2(8) . . ?
C29 C28 H28A 109.4 . . ?
N3 C28 H28A 109.4 . . ?
C29 C28 H28B 109.4 . . ?
N3 C28 H28B 109.4 . . ?
H28A C28 H28B 108.0 . . ?
C28 C29 C30 115.7(9) . . ?
C28 C29 H29A 108.3 . . ?
C30 C29 H29A 108.3 . . ?
C28 C29 H29B 108.3 . . ?
C30 C29 H29B 108.3 . . ?
H29A C29 H29B 107.4 . . ?
N4 C30 C29 109.8(8) . . ?
N4 C30 H30A 109.7 . . ?
C29 C30 H30A 109.7 . . ?
N4 C30 H30B 109.7 . . ?
C29 C30 H30B 109.7 . . ?
H30A C30 H30B 108.2 . . ?
N4 C31 C32 106.6(8) . . ?
N4 C31 H31A 110.4 . . ?
C32 C31 H31A 110.4 . . ?
N4 C31 H31B 110.4 . . ?
C32 C31 H31B 110.4 . . ?
H31A C31 H31B 108.6 . . ?
O4 C32 C31 109.0(7) . . ?
O4 C32 H32A 109.9 . . ?
C31 C32 H32A 109.9 . . ?
O4 C32 H32B 109.9 . . ?
C31 C32 H32B 109.9 . . ?
H32A C32 H32B 108.3 . . ?
O6 Mn3 O5 91.6(3) . . ?
O6 Mn3 N6 86.0(3) . . ?
O5 Mn3 N6 160.7(3) . . ?
O6 Mn3 N5 172.5(3) . . ?
O5 Mn3 N5 89.5(3) . . ?
N6 Mn3 N5 90.6(3) . . ?
O6 Mn3 N9 99.1(3) . . ?
O5 Mn3 N9 101.0(3) . . ?
N6 Mn3 N9 98.2(3) . . ?
N5 Mn3 N9 88.0(3) . . ?
O6 Mn3 O2 88.0(2) . 2_667 ?
O5 Mn3 O2 89.1(2) . 2_667 ?
N6 Mn3 O2 71.8(3) . 2_667 ?
N5 Mn3 O2 84.6(3) . 2_667 ?
N9 Mn3 O2 167.4(3) . 2_667 ?
C47 N5 C48 119.0(9) . . ?
C47 N5 Mn3 122.0(7) . . ?
C48 N5 Mn3 119.0(7) . . ?
C50 N6 C51 110.6(8) . . ?
C50 N6 Mn3 119.4(7) . . ?
C51 N6 Mn3 106.1(5) . . ?
C50 N6 H6A 106.7 . . ?
C51 N6 H6A 106.7 . . ?
Mn3 N6 H6A 106.7 . . ?
C41 O5 Mn3 128.3(6) . . ?
C52 O6 Mn3 111.0(5) . . ?
C52 O6 Mn2 108.6(5) . . ?
Mn3 O6 Mn2 138.7(3) . . ?
O5 C41 C42 121.7(9) . . ?
O5 C41 C46 121.8(10) . . ?
C42 C41 C46 116.4(11) . . ?
C43 C42 C41 124.3(12) . . ?
C43 C42 H42 117.9 . . ?
C41 C42 H42 117.9 . . ?
C42 C43 C44 119.2(12) . . ?
C42 C43 H43 120.4 . . ?
C44 C43 H43 120.4 . . ?
C45 C44 C43 117.8(12) . . ?
C45 C44 H44 121.1 . . ?
C43 C44 H44 121.1 . . ?
C44 C45 C46 121.9(12) . . ?
C44 C45 H45 119.1 . . ?
C46 C45 H45 119.1 . . ?
C41 C46 C45 120.4(11) . . ?
C41 C46 C47 122.5(10) . . ?
C45 C46 C47 117.1(11) . . ?
N5 C47 C46 127.8(10) . . ?
N5 C47 H47 116.1 . . ?
C46 C47 H47 116.1 . . ?
N5 C48 C49 113.2(9) . . ?
N5 C48 H48A 108.9 . . ?
C49 C48 H48A 108.9 . . ?
N5 C48 H48B 108.9 . . ?
C49 C48 H48B 108.9 . . ?
H48A C48 H48B 107.8 . . ?
C48 C49 C50 116.5(9) . . ?
C48 C49 H49A 108.2 . . ?
C50 C49 H49A 108.2 . . ?
C48 C49 H49B 108.2 . . ?
C50 C49 H49B 108.2 . . ?
H49A C49 H49B 107.3 . . ?
N6 C50 C49 108.3(9) . . ?
N6 C50 H50A 110.0 . . ?
C49 C50 H50A 110.0 . . ?
N6 C50 H50B 110.0 . . ?
C49 C50 H50B 110.0 . . ?
H50A C50 H50B 108.4 . . ?
C52 C51 N6 104.3(7) . . ?
C52 C51 H51A 110.9 . . ?
N6 C51 H51A 110.9 . . ?
C52 C51 H51B 110.9 . . ?
N6 C51 H51B 110.9 . . ?
H51A C51 H51B 108.9 . . ?
O6 C52 C51 109.7(7) . . ?
O6 C52 H52A 109.7 . . ?
C51 C52 H52A 109.7 . . ?
O6 C52 H52B 109.7 . . ?
C51 C52 H52B 109.7 . . ?
H52A C52 H52B 108.2 . . ?
C17 N7 Mn1 168.3(10) . . ?
N7 C17 S1 176.2(11) . . ?
C18 N8 Mn2 163.1(9) . . ?
N8 C18 S2 177.1(12) . . ?
C19 N9 Mn3 157.2(8) . . ?
N9 C19 S3 178.9(10) . . ?
H11 O1W H12 101.7 . . ?

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
O2 Mn1 O1 C1 -145.9(7) . . . . ?
N1 Mn1 O1 C1 31.0(7) . . . . ?
N2 Mn1 O1 C1 -66.3(14) . . . . ?
N7 Mn1 O1 C1 118.5(7) . . . . ?
O4 Mn1 O1 C1 -59.4(7) . . . . ?
O1 Mn1 O2 C12 149.9(6) . . . . ?
N2 Mn1 O2 C12 -14.5(6) . . . . ?
N7 Mn1 O2 C12 -109.6(6) . . . . ?
O4 Mn1 O2 C12 62.9(6) . . . . ?
Mn1 O1 C1 C2 156.0(7) . . . . ?
Mn1 O1 C1 C6 -25.1(12) . . . . ?
O1 C1 C2 C3 179.0(8) . . . . ?
C6 C1 C2 C3 0.1(14) . . . . ?
C1 C2 C3 C4 -1.1(17) . . . . ?
C2 C3 C4 C5 0.9(17) . . . . ?
C3 C4 C5 C6 0.1(16) . . . . ?
C4 C5 C6 C7 -177.9(10) . . . . ?
C4 C5 C6 C1 -0.9(15) . . . . ?
O1 C1 C6 C5 -178.0(8) . . . . ?
C2 C1 C6 C5 0.8(14) . . . . ?
O1 C1 C6 C7 -1.3(14) . . . . ?
C2 C1 C6 C7 177.5(9) . . . . ?
C8 N1 C7 C6 -176.2(10) . . . . ?
Mn1 N1 C7 C6 4.5(15) . . . . ?
C5 C6 C7 N1 -171.9(10) . . . . ?
C1 C6 C7 N1 11.4(17) . . . . ?
C7 N1 C8 C9 -125.5(11) . . . . ?
Mn1 N1 C8 C9 53.8(12) . . . . ?
N1 C8 C9 C10 -65.8(14) . . . . ?
C11 N2 C10 C9 176.7(9) . . . . ?
Mn1 N2 C10 C9 -55.1(12) . . . . ?
C8 C9 C10 N2 65.2(14) . . . . ?
C10 N2 C11 C12 172.4(9) . . . . ?
Mn1 N2 C11 C12 36.9(9) . . . . ?
Mn1 O2 C12 C11 40.4(9) . . . . ?
N2 C11 C12 O2 -51.3(10) . . . . ?
O4 Mn2 O3 C21 137.2(7) . . . . ?
N3 Mn2 O3 C21 -37.0(7) . . . . ?
N4 Mn2 O3 C21 56.4(14) . . . . ?
N8 Mn2 O3 C21 -126.4(7) . . . . ?
O6 Mn2 O3 C21 48.9(6) . . . . ?
O3 Mn2 O4 C32 -149.1(5) . . . . ?
N4 Mn2 O4 C32 16.2(5) . . . . ?
N8 Mn2 O4 C32 110.0(6) . . . . ?
O6 Mn2 O4 C32 -60.3(5) . . . . ?
O3 Mn2 O4 Mn1 48.2(4) . . . . ?
N4 Mn2 O4 Mn1 -146.5(4) . . . . ?
N8 Mn2 O4 Mn1 -52.6(5) . . . . ?
O6 Mn2 O4 Mn1 137.1(4) . . . . ?
Mn2 O3 C21 C22 -151.8(7) . . . . ?
Mn2 O3 C21 C26 28.6(11) . . . . ?
O3 C21 C22 C23 179.2(9) . . . . ?
C26 C21 C22 C23 -1.3(14) . . . . ?
C21 C22 C23 C24 2.1(16) . . . . ?
C22 C23 C24 C25 -1.2(16) . . . . ?
C23 C24 C25 C26 -0.4(16) . . . . ?
C24 C25 C26 C21 1.1(15) . . . . ?
C24 C25 C26 C27 177.2(9) . . . . ?
O3 C21 C26 C25 179.3(8) . . . . ?
C22 C21 C26 C25 -0.3(13) . . . . ?
O3 C21 C26 C27 3.2(13) . . . . ?
C22 C21 C26 C27 -176.3(8) . . . . ?
C28 N3 C27 C26 175.2(9) . . . . ?
Mn2 N3 C27 C26 -4.2(14) . . . . ?
C25 C26 C27 N3 168.5(9) . . . . ?
C21 C26 C27 N3 -15.5(15) . . . . ?
C27 N3 C28 C29 125.6(10) . . . . ?
Mn2 N3 C28 C29 -55.0(10) . . . . ?
N3 C28 C29 C30 65.8(11) . . . . ?
C31 N4 C30 C29 -175.0(8) . . . . ?
Mn2 N4 C30 C29 59.1(9) . . . . ?
C28 C29 C30 N4 -68.3(11) . . . . ?
C30 N4 C31 C32 -170.2(7) . . . . ?
Mn2 N4 C31 C32 -37.2(8) . . . . ?
Mn2 O4 C32 C31 -42.0(8) . . . . ?
Mn1 O4 C32 C31 125.9(6) . . . . ?
N4 C31 C32 O4 53.2(9) . . . . ?
O6 Mn3 O5 C41 -141.7(8) . . . . ?
N6 Mn3 O5 C41 -59.5(13) . . . . ?
N5 Mn3 O5 C41 30.8(8) . . . . ?
N9 Mn3 O5 C41 118.7(8) . . . . ?
O2 Mn3 O5 C41 -53.8(7) 2_667 . . . ?
O5 Mn3 O6 C52 145.6(6) . . . . ?
N6 Mn3 O6 C52 -15.3(6) . . . . ?
N9 Mn3 O6 C52 -113.0(6) . . . . ?
O2 Mn3 O6 C52 56.6(5) 2_667 . . . ?
O5 Mn3 O6 Mn2 -51.6(4) . . . . ?
N6 Mn3 O6 Mn2 147.5(5) . . . . ?
N9 Mn3 O6 Mn2 49.8(5) . . . . ?
O2 Mn3 O6 Mn2 -140.6(4) 2_667 . . . ?
Mn3 O5 C41 C42 158.5(8) . . . . ?
Mn3 O5 C41 C46 -21.7(13) . . . . ?
O5 C41 C42 C43 -176.2(10) . . . . ?
C46 C41 C42 C43 4.0(16) . . . . ?
C41 C42 C43 C44 -3.4(19) . . . . ?
C42 C43 C44 C45 1.8(19) . . . . ?
C43 C44 C45 C46 -1.2(19) . . . . ?
O5 C41 C46 C45 177.0(9) . . . . ?
C42 C41 C46 C45 -3.1(14) . . . . ?
O5 C41 C46 C47 -5.4(14) . . . . ?
C42 C41 C46 C47 174.4(9) . . . . ?
C44 C45 C46 C41 1.9(17) . . . . ?
C44 C45 C46 C47 -175.8(11) . . . . ?
C48 N5 C47 C46 -172.2(9) . . . . ?
Mn3 N5 C47 C46 7.8(14) . . . . ?
C41 C46 C47 N5 11.7(16) . . . . ?
C45 C46 C47 N5 -170.7(10) . . . . ?
C47 N5 C48 C49 -124.9(11) . . . . ?
Mn3 N5 C48 C49 55.1(11) . . . . ?
N5 C48 C49 C50 -63.4(13) . . . . ?
C51 N6 C50 C49 175.1(7) . . . . ?
Mn3 N6 C50 C49 -61.3(10) . . . . ?
C48 C49 C50 N6 65.2(12) . . . . ?
C50 N6 C51 C52 168.2(7) . . . . ?
Mn3 N6 C51 C52 37.3(8) . . . . ?
Mn3 O6 C52 C51 42.3(9) . . . . ?
Mn2 O6 C52 C51 -125.8(6) . . . . ?
N6 C51 C52 O6 -52.3(9) . . . . ?

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
_geom_hbond_publ_flag
N2 H2A O3 0.98 2.02 2.981(10) 165.3 . yes
N2 H2A O4 0.98 2.38 2.976(10) 118.7 . yes
C7 H7 S2 0.93 3.01 3.690(11) 131.6 . yes
C9 H9A S3 0.97 3.01 3.867(11) 147.5 2_766 yes
C12 H12B O5 0.97 2.59 3.365(11) 136.7 2_667 yes
N4 H4A O5 0.98 2.06 3.022(10) 165.4 . yes
N4 H4A O6 0.98 2.37 2.965(9) 118.6 . yes
C32 H32A O1 0.97 2.45 3.192(11) 133.0 . yes
N6 H6A O1 0.98 2.11 3.049(10) 160.8 2_667 yes
N6 H6A O2 0.98 2.28 2.930(10) 123.1 2_667 yes
C52 H52B O3 0.97 2.55 3.279(11) 131.8 . yes

_refine_diff_density_max         0.995
_refine_diff_density_min         -0.477
_refine_diff_density_rms         0.112

####################################################################### 
# 
# 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_Complex_1
_database_code_depnum_ccdc_archive 'CCDC 1934500'
loop_
_audit_author_name
_audit_author_address
'Ennio Zangrando'
;TRIESTE Italy
Italy
;
_audit_update_record             
;
2020-03-18 deposited with the CCDC.	2020-04-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H20 Mn N2 O4, Cl'
_chemical_formula_sum            'C12 H20 Cl Mn N2 O4'
_chemical_formula_weight         346.69

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'
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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

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

_cell_length_a                   18.4286(4)
_cell_length_b                   7.7670(2)
_cell_length_c                   20.6985(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2962.68(12)
_cell_formula_units_Z            8
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9866
_cell_measurement_theta_min      2.21
_cell_measurement_theta_max      27.98

_exptl_crystal_description       Block
_exptl_crystal_colour            Black
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.555
_exptl_crystal_F_000             1440
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.28
_exptl_absorpt_coefficient_mu    1.085
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.701
_exptl_absorpt_correction_T_max  0.758
_exptl_absorpt_process_details   'BRUKER SADABS'

_exptl_absorpt_special_details   ?

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            43903
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_theta_min         1.968
_diffrn_reflns_theta_max         28.135
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3615
_reflns_number_gt                2911
_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.
 
 _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 SMART'
_computing_cell_refinement       'BRUKER SMART'
_computing_data_reduction        'BRUKER SAINT'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    
'Diamond. Ver. 3.2k. (Putz & Brandernburg, 2014)'
_computing_publication_material  'WinGX publication routines (Farrugia, 2012)'

_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)+(0.0326P)²+1.1740P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3615
_refine_ls_number_parameters     196
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0412
_refine_ls_R_factor_gt           0.0281
_refine_ls_wR_factor_ref         0.0728
_refine_ls_wR_factor_gt          0.0672
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_restrained_S_all      1.044
_refine_ls_shift/su_max          0.002
_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 0.57774(2) 0.67868(3) 0.29813(2) 0.02192(8) Uani 1 1 d . . . . .
Cl1 Cl 0.58429(3) 0.22316(6) 0.42406(2) 0.04337(13) Uani 1 1 d . . . . .
O1 O 0.58656(6) 0.69850(15) 0.20818(5) 0.0280(3) Uani 1 1 d . . . . .
O2 O 0.47545(6) 0.66453(15) 0.29287(5) 0.0291(3) Uani 1 1 d . . . . .
O3 O 0.59095(7) 0.39027(16) 0.28888(6) 0.0325(3) Uani 1 1 d D . . . .
H3A H 0.5675(11) 0.333(3) 0.2624(10) 0.049 Uiso 1 1 d D U . . .
H3B H 0.5862(11) 0.339(3) 0.3234(9) 0.049 Uiso 1 1 d D U . . .
O4 O 0.57784(8) 0.96624(16) 0.30668(7) 0.0401(3) Uani 1 1 d D . . . .
H4A H 0.5735(12) 1.019(3) 0.3404(9) 0.060 Uiso 1 1 d D U . . .
H4B H 0.5612(12) 1.021(3) 0.2766(10) 0.060 Uiso 1 1 d D U . . .
N1 N 0.68627(7) 0.68743(17) 0.30823(6) 0.0263(3) Uani 1 1 d . . . . .
N2 N 0.56251(8) 0.64361(19) 0.39572(7) 0.0277(3) Uani 1 1 d . . . . .
H2A H 0.5661(10) 0.540(3) 0.4023(9) 0.033 Uiso 1 1 d . U . . .
C1 C 0.63661(9) 0.6148(2) 0.17463(8) 0.0252(3) Uani 1 1 d . . . . .
C2 C 0.62237(10) 0.5715(2) 0.11021(8) 0.0317(4) Uani 1 1 d . . . . .
H2 H 0.578333 0.602805 0.091662 0.038 Uiso 1 1 calc R U . . .
C3 C 0.67275(11) 0.4832(2) 0.07397(9) 0.0403(4) Uani 1 1 d . . . . .
H3 H 0.661760 0.452841 0.031618 0.048 Uiso 1 1 calc R U . . .
C4 C 0.73991(11) 0.4386(2) 0.09983(9) 0.0428(5) Uani 1 1 d . . . . .
H4 H 0.773421 0.377624 0.075210 0.051 Uiso 1 1 calc R U . . .
C5 C 0.75598(10) 0.4855(2) 0.16185(9) 0.0350(4) Uani 1 1 d . . . . .
H5 H 0.801373 0.458826 0.178737 0.042 Uiso 1 1 calc R U . . .
C6 C 0.70555(9) 0.5728(2) 0.20061(8) 0.0271(3) Uani 1 1 d . . . . .
C7 C 0.72799(9) 0.6299(2) 0.26353(8) 0.0292(4) Uani 1 1 d . . . . .
H7 H 0.777338 0.624769 0.272715 0.035 Uiso 1 1 calc R U . . .
C8 C 0.71919(10) 0.7612(3) 0.36677(8) 0.0363(4) Uani 1 1 d . . . . .
H8A H 0.709969 0.884103 0.367465 0.044 Uiso 1 1 calc R U . . .
H8B H 0.771324 0.744686 0.364837 0.044 Uiso 1 1 calc R U . . .
C9 C 0.69089(10) 0.6827(2) 0.42884(9) 0.0378(4) Uani 1 1 d . . . . .
H9A H 0.696205 0.558657 0.426424 0.045 Uiso 1 1 calc R U . . .
H9B H 0.720561 0.723045 0.464475 0.045 Uiso 1 1 calc R U . . .
C10 C 0.61232(10) 0.7248(2) 0.44311(8) 0.0349(4) Uani 1 1 d . . . . .
H10A H 0.600241 0.684901 0.486194 0.042 Uiso 1 1 calc R U . . .
H10B H 0.605722 0.848695 0.442110 0.042 Uiso 1 1 calc R U . . .
C11 C 0.48572(10) 0.6918(3) 0.40749(9) 0.0385(4) Uani 1 1 d . . . . .
H11A H 0.480928 0.816032 0.409552 0.046 Uiso 1 1 calc R U . . .
H11B H 0.469186 0.643635 0.448150 0.046 Uiso 1 1 calc R U . . .
C12 C 0.44116(10) 0.6213(3) 0.35243(9) 0.0375(4) Uani 1 1 d . . . . .
H12A H 0.437110 0.497236 0.356323 0.045 Uiso 1 1 calc R U . . .
H12B H 0.392697 0.669943 0.353693 0.045 Uiso 1 1 calc R U . . .


_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 1.8754(11) . ?
Mn1 O2 1.8914(11) . ?
Mn1 N1 2.0121(13) . ?
Mn1 N2 2.0573(14) . ?
Mn1 O4 2.2405(13) . ?
Mn1 O3 2.2615(13) . ?
O1 C1 1.3248(19) . ?
O2 C12 1.425(2) . ?
O3 H3A 0.828(15) . ?
O3 H3B 0.823(16) . ?
O4 H4A 0.814(16) . ?
O4 H4B 0.815(16) . ?
N1 C7 1.283(2) . ?
N1 C8 1.471(2) . ?
N2 C11 1.484(2) . ?
N2 C10 1.484(2) . ?
N2 H2A 0.82(2) . ?
C1 C2 1.400(2) . ?
C1 C6 1.418(2) . ?
C2 C3 1.377(3) . ?
C2 H2 0.9300 . ?
C3 C4 1.392(3) . ?
C3 H3 0.9300 . ?
C4 C5 1.367(3) . ?
C4 H4 0.9300 . ?
C5 C6 1.403(2) . ?
C5 H5 0.9300 . ?
C6 C7 1.437(2) . ?
C7 H7 0.9300 . ?
C8 C9 1.514(3) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C9 C10 1.514(3) . ?
C9 H9A 0.9700 . ?
C9 H9B 0.9700 . ?
C10 H10A 0.9700 . ?
C10 H10B 0.9700 . ?
C11 C12 1.508(3) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?

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 O2 91.95(5) . . ?
O1 Mn1 N1 90.81(5) . . ?
O2 Mn1 N1 177.00(5) . . ?
O1 Mn1 N2 175.90(6) . . ?
O2 Mn1 N2 85.00(5) . . ?
N1 Mn1 N2 92.18(6) . . ?
O1 Mn1 O4 89.80(5) . . ?
O2 Mn1 O4 93.63(5) . . ?
N1 Mn1 O4 87.55(5) . . ?
N2 Mn1 O4 93.13(6) . . ?
O1 Mn1 O3 89.30(5) . . ?
O2 Mn1 O3 92.57(5) . . ?
N1 Mn1 O3 86.28(5) . . ?
N2 Mn1 O3 88.09(5) . . ?
O4 Mn1 O3 173.76(5) . . ?
C1 O1 Mn1 122.71(10) . . ?
C12 O2 Mn1 113.94(10) . . ?
Mn1 O3 H3A 122.2(15) . . ?
Mn1 O3 H3B 113.1(16) . . ?
H3A O3 H3B 105(2) . . ?
Mn1 O4 H4A 124.9(17) . . ?
Mn1 O4 H4B 117.3(17) . . ?
H4A O4 H4B 111(2) . . ?
C7 N1 C8 118.83(14) . . ?
C7 N1 Mn1 120.59(11) . . ?
C8 N1 Mn1 120.58(11) . . ?
C11 N2 C10 111.97(14) . . ?
C11 N2 Mn1 104.95(10) . . ?
C10 N2 Mn1 120.55(12) . . ?
C11 N2 H2A 107.3(13) . . ?
C10 N2 H2A 104.9(13) . . ?
Mn1 N2 H2A 106.4(14) . . ?
O1 C1 C2 119.11(15) . . ?
O1 C1 C6 122.55(14) . . ?
C2 C1 C6 118.29(15) . . ?
C3 C2 C1 120.81(16) . . ?
C3 C2 H2 119.6 . . ?
C1 C2 H2 119.6 . . ?
C2 C3 C4 120.94(17) . . ?
C2 C3 H3 119.5 . . ?
C4 C3 H3 119.5 . . ?
C5 C4 C3 119.16(17) . . ?
C5 C4 H4 120.4 . . ?
C3 C4 H4 120.4 . . ?
C4 C5 C6 121.51(17) . . ?
C4 C5 H5 119.2 . . ?
C6 C5 H5 119.2 . . ?
C5 C6 C1 119.21(15) . . ?
C5 C6 C7 118.50(15) . . ?
C1 C6 C7 122.06(15) . . ?
N1 C7 C6 126.06(15) . . ?
N1 C7 H7 117.0 . . ?
C6 C7 H7 117.0 . . ?
N1 C8 C9 113.58(14) . . ?
N1 C8 H8A 108.8 . . ?
C9 C8 H8A 108.8 . . ?
N1 C8 H8B 108.8 . . ?
C9 C8 H8B 108.8 . . ?
H8A C8 H8B 107.7 . . ?
C10 C9 C8 114.09(15) . . ?
C10 C9 H9A 108.7 . . ?
C8 C9 H9A 108.7 . . ?
C10 C9 H9B 108.7 . . ?
C8 C9 H9B 108.7 . . ?
H9A C9 H9B 107.6 . . ?
N2 C10 C9 111.77(14) . . ?
N2 C10 H10A 109.3 . . ?
C9 C10 H10A 109.3 . . ?
N2 C10 H10B 109.3 . . ?
C9 C10 H10B 109.3 . . ?
H10A C10 H10B 107.9 . . ?
N2 C11 C12 107.68(14) . . ?
N2 C11 H11A 110.2 . . ?
C12 C11 H11A 110.2 . . ?
N2 C11 H11B 110.2 . . ?
C12 C11 H11B 110.2 . . ?
H11A C11 H11B 108.5 . . ?
O2 C12 C11 109.08(15) . . ?
O2 C12 H12A 109.9 . . ?
C11 C12 H12A 109.9 . . ?
O2 C12 H12B 109.9 . . ?
C11 C12 H12B 109.9 . . ?
H12A C12 H12B 108.3 . . ?

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
O2 Mn1 O1 C1 -137.17(12) . . . . ?
N1 Mn1 O1 C1 41.66(12) . . . . ?
O4 Mn1 O1 C1 129.21(12) . . . . ?
O3 Mn1 O1 C1 -44.62(12) . . . . ?
O1 Mn1 O2 C12 171.18(12) . . . . ?
N2 Mn1 O2 C12 -6.07(12) . . . . ?
O4 Mn1 O2 C12 -98.90(12) . . . . ?
O3 Mn1 O2 C12 81.79(12) . . . . ?
Mn1 O1 C1 C2 151.62(12) . . . . ?
Mn1 O1 C1 C6 -30.9(2) . . . . ?
O1 C1 C2 C3 -179.40(16) . . . . ?
C6 C1 C2 C3 3.0(2) . . . . ?
C1 C2 C3 C4 -1.7(3) . . . . ?
C2 C3 C4 C5 -0.8(3) . . . . ?
C3 C4 C5 C6 1.9(3) . . . . ?
C4 C5 C6 C1 -0.6(3) . . . . ?
C4 C5 C6 C7 -175.23(17) . . . . ?
O1 C1 C6 C5 -179.37(15) . . . . ?
C2 C1 C6 C5 -1.9(2) . . . . ?
O1 C1 C6 C7 -4.9(2) . . . . ?
C2 C1 C6 C7 172.56(15) . . . . ?
C8 N1 C7 C6 -172.24(16) . . . . ?
Mn1 N1 C7 C6 7.3(2) . . . . ?
C5 C6 C7 N1 -168.75(17) . . . . ?
C1 C6 C7 N1 16.8(3) . . . . ?
C7 N1 C8 C9 -127.18(18) . . . . ?
Mn1 N1 C8 C9 53.33(19) . . . . ?
N1 C8 C9 C10 -68.0(2) . . . . ?
C11 N2 C10 C9 -177.06(15) . . . . ?
Mn1 N2 C10 C9 -52.93(18) . . . . ?
C8 C9 C10 N2 67.2(2) . . . . ?
C10 N2 C11 C12 173.12(15) . . . . ?
Mn1 N2 C11 C12 40.67(17) . . . . ?
Mn1 O2 C12 C11 31.03(18) . . . . ?
N2 C11 C12 O2 -47.8(2) . . . . ?

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
_geom_hbond_publ_flag
O3 H3A O2 0.828(15) 1.909(16) 2.7267(17) 169(2) 3_645 yes
O3 H3B Cl1 0.823(16) 2.270(16) 3.0868(13) 172(2) . yes
O4 H4A Cl1 0.814(16) 2.355(17) 3.1461(14) 164(2) 1_565 yes
O4 H4B O2 0.815(16) 1.940(16) 2.7537(17) 176(2) 3_655 yes
N2 H2A Cl1 0.82(2) 2.52(2) 3.3422(15) 176.9(18) . yes
C8 H8B Cl1 0.97 2.93 3.8220(19) 152.7 6_765 yes
C10 H10B Cl1 0.97 2.96 3.9247(19) 173.9 1_565 yes

_refine_diff_density_max         0.339
_refine_diff_density_min         -0.260
_refine_diff_density_rms         0.052

