# 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_ymd808_a
_database_code_depnum_ccdc_archive 'CCDC 1969921'
loop_
_audit_author_name
_audit_author_address
'Michelle C. Neary'
;Hunter College, City University of New York
United States of America
;
_audit_update_record             
;
2019-12-03 deposited with the CCDC.	2020-01-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H18 Cl2 Mn N4 O2'
_chemical_formula_weight         472.22

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn -0.5299 2.8052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2/n

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y, -z+1/2'
'-x, -y, -z'
'x-1/2, -y, z-1/2'

_cell_length_a                   8.9559(9)
_cell_length_b                   11.5794(11)
_cell_length_c                   10.6239(11)
_cell_angle_alpha                90.00
_cell_angle_beta                 114.012(5)
_cell_angle_gamma                90.00
_cell_volume                     1006.40(17)
_cell_formula_units_Z            2
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    6955
_cell_measurement_theta_min      3.82
_cell_measurement_theta_max      69.21

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.558
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             482
_exptl_absorpt_coefficient_mu    7.987
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.3438
_exptl_absorpt_correction_T_max  0.5022
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      200(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_radiation_source         'MICRO fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker CMOS'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            11286
_diffrn_reflns_av_R_equivalents  0.0584
_diffrn_reflns_av_sigmaI/netI    0.0381
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.82
_diffrn_reflns_theta_max         69.24
_reflns_number_total             1762
_reflns_number_gt                1487
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0434P)²+3.9610P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         1762
_refine_ls_number_parameters     140
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0692
_refine_ls_R_factor_gt           0.0557
_refine_ls_wR_factor_ref         0.1400
_refine_ls_wR_factor_gt          0.1286
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_restrained_S_all      1.074
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn1 Mn 0.2500 0.24315(7) 0.7500 0.0258(3) Uani 1 2 d S . .
Cl1 Cl 0.27161(15) 0.24059(9) 0.52122(12) 0.0354(3) Uani 1 1 d . . .
N1 N 0.5138(4) 0.3047(3) 0.8467(4) 0.0281(8) Uani 1 1 d . . .
N2 N 0.2500 0.4367(4) 0.7500 0.0230(10) Uani 1 2 d S . .
N3 N 0.2500 1.0468(4) 0.7500 0.0302(12) Uani 1 2 d S . .
C1 C 0.6424(6) 0.2335(4) 0.8870(5) 0.0311(10) Uani 1 1 d . . .
H1A H 0.6230 0.1527 0.8858 0.037 Uiso 1 1 calc R . .
C2 C 0.8007(6) 0.2709(4) 0.9300(5) 0.0338(10) Uani 1 1 d . . .
H2A H 0.8889 0.2177 0.9551 0.041 Uiso 1 1 calc R . .
C3 C 0.8276(6) 0.3875(4) 0.9355(5) 0.0388(11) Uani 1 1 d . . .
H3B H 0.9361 0.4163 0.9667 0.047 Uiso 1 1 calc R . .
C4 C 0.6975(6) 0.4639(4) 0.8958(5) 0.0342(11) Uani 1 1 d . . .
H4A H 0.7154 0.5449 0.8995 0.041 Uiso 1 1 calc R . .
C5 C 0.5403(5) 0.4193(3) 0.8504(4) 0.0254(9) Uani 1 1 d . . .
C6 C 0.3923(5) 0.4942(3) 0.7998(4) 0.0260(9) Uani 1 1 d . . .
C7 C 0.3965(5) 0.6134(3) 0.8025(4) 0.0263(9) Uani 1 1 d . . .
H7A H 0.4983 0.6529 0.8399 0.032 Uiso 1 1 calc R . .
C8 C 0.2500 0.6757(5) 0.7500 0.0269(13) Uani 1 2 d S . .
C9 C 0.2500 0.8038(5) 0.7500 0.0269(13) Uani 1 2 d S . .
C10 C 0.3729(6) 0.8672(4) 0.7335(5) 0.0351(11) Uani 1 1 d . . .
H10A H 0.4619 0.8287 0.7249 0.042 Uiso 1 1 calc R . .
C11 C 0.3650(6) 0.9861(4) 0.7298(5) 0.0357(11) Uani 1 1 d . . .
H11A H 0.4461 1.0272 0.7119 0.043 Uiso 1 1 calc R . .
O1 O 0.3349(5) 0.0136(3) 0.3936(5) 0.0538(10) Uani 1 1 d D . .
H1WB H 0.299(7) 0.076(3) 0.418(6) 0.081 Uiso 1 1 d D . .
H1WA H 0.4395(19) 0.012(6) 0.441(6) 0.081 Uiso 1 1 d D . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Mn1 N2 2.242(4) . ?
Mn1 N3 2.273(5) 1_545 ?
Mn1 N1 2.274(4) . ?
Mn1 N1 2.274(4) 2_556 ?
Mn1 Cl1 2.5156(11) 2_556 ?
Mn1 Cl1 2.5157(11) . ?
N1 C1 1.337(6) . ?
N1 C5 1.346(5) . ?
N2 C6 1.341(5) 2_556 ?
N2 C6 1.341(5) . ?
N3 C11 1.334(5) 2_556 ?
N3 C11 1.334(5) . ?
N3 Mn1 2.273(5) 1_565 ?
C1 C2 1.371(7) . ?
C1 H1A 0.9500 . ?
C2 C3 1.369(6) . ?
C2 H2A 0.9500 . ?
C3 C4 1.384(7) . ?
C3 H3B 0.9500 . ?
C4 C5 1.389(6) . ?
C4 H4A 0.9500 . ?
C5 C6 1.490(6) . ?
C6 C7 1.381(6) . ?
C7 C8 1.399(5) . ?
C7 H7A 0.9500 . ?
C8 C7 1.399(5) 2_556 ?
C8 C9 1.483(8) . ?
C9 C10 1.392(6) . ?
C9 C10 1.392(6) 2_556 ?
C10 C11 1.378(6) . ?
C10 H10A 0.9500 . ?
C11 H11A 0.9500 . ?
O1 H1WB 0.869(10) . ?
O1 H1WA 0.865(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
N2 Mn1 N3 180.000(1) . 1_545 ?
N2 Mn1 N1 71.73(9) . . ?
N3 Mn1 N1 108.27(9) 1_545 . ?
N2 Mn1 N1 71.73(9) . 2_556 ?
N3 Mn1 N1 108.27(9) 1_545 2_556 ?
N1 Mn1 N1 143.46(18) . 2_556 ?
N2 Mn1 Cl1 90.68(3) . 2_556 ?
N3 Mn1 Cl1 89.32(3) 1_545 2_556 ?
N1 Mn1 Cl1 92.37(10) . 2_556 ?
N1 Mn1 Cl1 88.05(10) 2_556 2_556 ?
N2 Mn1 Cl1 90.68(3) . . ?
N3 Mn1 Cl1 89.32(3) 1_545 . ?
N1 Mn1 Cl1 88.05(10) . . ?
N1 Mn1 Cl1 92.37(10) 2_556 . ?
Cl1 Mn1 Cl1 178.65(6) 2_556 . ?
C1 N1 C5 118.7(4) . . ?
C1 N1 Mn1 123.5(3) . . ?
C5 N1 Mn1 117.4(3) . . ?
C6 N2 C6 120.5(5) 2_556 . ?
C6 N2 Mn1 119.8(2) 2_556 . ?
C6 N2 Mn1 119.8(2) . . ?
C11 N3 C11 116.4(5) 2_556 . ?
C11 N3 Mn1 121.8(3) 2_556 1_565 ?
C11 N3 Mn1 121.8(3) . 1_565 ?
N1 C1 C2 123.4(4) . . ?
N1 C1 H1A 118.3 . . ?
C2 C1 H1A 118.3 . . ?
C3 C2 C1 117.8(4) . . ?
C3 C2 H2A 121.1 . . ?
C1 C2 H2A 121.1 . . ?
C2 C3 C4 120.4(5) . . ?
C2 C3 H3B 119.8 . . ?
C4 C3 H3B 119.8 . . ?
C3 C4 C5 118.5(4) . . ?
C3 C4 H4A 120.8 . . ?
C5 C4 H4A 120.8 . . ?
N1 C5 C4 121.2(4) . . ?
N1 C5 C6 116.3(4) . . ?
C4 C5 C6 122.4(4) . . ?
N2 C6 C7 121.2(4) . . ?
N2 C6 C5 114.6(4) . . ?
C7 C6 C5 124.2(4) . . ?
C6 C7 C8 119.5(4) . . ?
C6 C7 H7A 120.2 . . ?
C8 C7 H7A 120.2 . . ?
C7 C8 C7 118.0(5) 2_556 . ?
C7 C8 C9 121.0(3) 2_556 . ?
C7 C8 C9 121.0(3) . . ?
C10 C9 C10 116.3(5) . 2_556 ?
C10 C9 C8 121.9(3) . . ?
C10 C9 C8 121.9(3) 2_556 . ?
C11 C10 C9 119.8(5) . . ?
C11 C10 H10A 120.1 . . ?
C9 C10 H10A 120.1 . . ?
N3 C11 C10 123.7(5) . . ?
N3 C11 H11A 118.1 . . ?
C10 C11 H11A 118.1 . . ?
H1WB O1 H1WA 107(2) . . ?

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
N2 Mn1 N1 C1 -176.3(4) . . . . ?
N3 Mn1 N1 C1 3.7(4) 1_545 . . . ?
N1 Mn1 N1 C1 -176.3(4) 2_556 . . . ?
Cl1 Mn1 N1 C1 93.8(4) 2_556 . . . ?
Cl1 Mn1 N1 C1 -84.9(4) . . . . ?
N2 Mn1 N1 C5 -3.1(3) . . . . ?
N3 Mn1 N1 C5 176.9(3) 1_545 . . . ?
N1 Mn1 N1 C5 -3.1(3) 2_556 . . . ?
Cl1 Mn1 N1 C5 -93.0(3) 2_556 . . . ?
Cl1 Mn1 N1 C5 88.2(3) . . . . ?
N3 Mn1 N2 C6 -25(100) 1_545 . . 2_556 ?
N1 Mn1 N2 C6 -178.8(2) . . . 2_556 ?
N1 Mn1 N2 C6 1.2(2) 2_556 . . 2_556 ?
Cl1 Mn1 N2 C6 -86.5(2) 2_556 . . 2_556 ?
Cl1 Mn1 N2 C6 93.5(2) . . . 2_556 ?
N3 Mn1 N2 C6 155(100) 1_545 . . . ?
N1 Mn1 N2 C6 1.2(2) . . . . ?
N1 Mn1 N2 C6 -178.8(2) 2_556 . . . ?
Cl1 Mn1 N2 C6 93.5(2) 2_556 . . . ?
Cl1 Mn1 N2 C6 -86.5(2) . . . . ?
C5 N1 C1 C2 -1.1(7) . . . . ?
Mn1 N1 C1 C2 172.0(4) . . . . ?
N1 C1 C2 C3 2.0(7) . . . . ?
C1 C2 C3 C4 -1.4(8) . . . . ?
C2 C3 C4 C5 -0.1(8) . . . . ?
C1 N1 C5 C4 -0.5(7) . . . . ?
Mn1 N1 C5 C4 -174.0(3) . . . . ?
C1 N1 C5 C6 178.0(4) . . . . ?
Mn1 N1 C5 C6 4.5(5) . . . . ?
C3 C4 C5 N1 1.0(7) . . . . ?
C3 C4 C5 C6 -177.3(4) . . . . ?
C6 N2 C6 C7 0.6(3) 2_556 . . . ?
Mn1 N2 C6 C7 -179.4(3) . . . . ?
C6 N2 C6 C5 -179.4(4) 2_556 . . . ?
Mn1 N2 C6 C5 0.6(4) . . . . ?
N1 C5 C6 N2 -3.4(5) . . . . ?
C4 C5 C6 N2 175.1(4) . . . . ?
N1 C5 C6 C7 176.6(4) . . . . ?
C4 C5 C6 C7 -5.0(7) . . . . ?
N2 C6 C7 C8 -1.3(6) . . . . ?
C5 C6 C7 C8 178.8(3) . . . . ?
C6 C7 C8 C7 0.6(3) . . . 2_556 ?
C6 C7 C8 C9 -179.4(3) . . . . ?
C7 C8 C9 C10 -147.1(3) 2_556 . . . ?
C7 C8 C9 C10 32.9(3) . . . . ?
C7 C8 C9 C10 32.9(3) 2_556 . . 2_556 ?
C7 C8 C9 C10 -147.1(3) . . . 2_556 ?
C10 C9 C10 C11 -2.1(4) 2_556 . . . ?
C8 C9 C10 C11 177.9(4) . . . . ?
C11 N3 C11 C10 -2.2(4) 2_556 . . . ?
Mn1 N3 C11 C10 177.8(4) 1_565 . . . ?
C9 C10 C11 N3 4.4(8) . . . . ?

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
C2 H2A Cl1 0.95 2.96 3.667(5) 132.3 2_656
C4 H4A Cl1 0.95 2.75 3.634(4) 155.1 4_666
C7 H7A Cl1 0.95 2.72 3.631(5) 161.5 4_666
O1 H1WB Cl1 0.869(10) 2.26(2) 3.113(4) 165(5) .
O1 H1WA O1 0.865(10) 2.09(3) 2.918(9) 160(7) 3_656

_diffrn_measured_fraction_theta_max 0.936
_diffrn_reflns_theta_full        68.25
_diffrn_measured_fraction_theta_full 0.943
_refine_diff_density_max         0.596
_refine_diff_density_min         -0.400
_refine_diff_density_rms         0.082
####################################################################### 
# 
# 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_gz1477
_database_code_depnum_ccdc_archive 'CCDC 1969922'
loop_
_audit_author_name
_audit_author_address
'Michelle C. Neary'
;Hunter College, City University of New York
United States of America
;
_audit_update_record             
;
2019-12-03 deposited with the CCDC.	2020-01-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2017/1
_shelx_SHELXL_version_number     2017/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C20 H14 Br2 Mn N4, C H4 O'
_chemical_formula_sum            'C21 H18 Br2 Mn N4 O'
_chemical_formula_weight         557.15

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'
Br Br -0.2901 2.4595 '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                   8.8113(2)
_cell_length_b                   10.2327(3)
_cell_length_c                   11.4867(3)
_cell_angle_alpha                95.1760(10)
_cell_angle_beta                 91.4490(10)
_cell_angle_gamma                94.4070(10)
_cell_volume                     1027.87(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    130(2)
_cell_measurement_reflns_used    9790
_cell_measurement_theta_min      2.56
_cell_measurement_theta_max      36.85

_exptl_crystal_description       plate
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.800
_exptl_crystal_F_000             550
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.360
_exptl_crystal_size_mid          0.250
_exptl_crystal_size_min          0.060
_exptl_absorpt_coefficient_mu    4.550
_shelx_estimated_absorpt_T_min   0.291
_shelx_estimated_absorpt_T_max   0.772
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.4944
_exptl_absorpt_correction_T_max  0.7472
_exptl_absorpt_process_details   sadabs
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      130(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            45159
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         2.556
_diffrn_reflns_theta_max         36.902
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             10067
_reflns_number_gt                7782
_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 APEX3'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_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)+(0.0258P)²+0.9754P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_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         10067
_refine_ls_number_parameters     267
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0535
_refine_ls_R_factor_gt           0.0328
_refine_ls_wR_factor_ref         0.0726
_refine_ls_wR_factor_gt          0.0667
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_restrained_S_all      1.037
_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 0.70533(3) 0.73445(2) 0.26422(2) 0.01040(4) Uani 1 1 d . . . . .
Br1 Br 0.60903(2) 0.97493(2) 0.28245(2) 0.01520(4) Uani 1 1 d . . . . .
Br2 Br 0.79448(2) 0.48018(2) 0.23136(2) 0.01675(4) Uani 1 1 d . . . . .
N1 N 0.47468(15) 0.65448(13) 0.31576(11) 0.0115(2) Uani 1 1 d . . . . .
N2 N 0.71213(14) 0.72940(12) 0.45662(10) 0.0095(2) Uani 1 1 d . . . . .
N3 N 0.94100(15) 0.81174(13) 0.33192(11) 0.0114(2) Uani 1 1 d . . . . .
N4 N 0.71080(16) 0.73765(14) 1.07050(11) 0.0138(2) Uani 1 1 d . . . . .
C11 C 0.35696(18) 0.62053(16) 0.24031(13) 0.0142(3) Uani 1 1 d . . . . .
H11A H 0.373227 0.623804 0.159144 0.017 Uiso 1 1 calc R U . . .
C12 C 0.21246(18) 0.58083(16) 0.27508(14) 0.0147(3) Uani 1 1 d . . . . .
H12A H 0.130573 0.560894 0.219345 0.018 Uiso 1 1 calc R U . . .
C13 C 0.19028(18) 0.57092(16) 0.39285(14) 0.0146(3) Uani 1 1 d . . . . .
H13A H 0.093417 0.540804 0.418940 0.017 Uiso 1 1 calc R U . . .
C14 C 0.31075(17) 0.60536(15) 0.47244(13) 0.0128(3) Uani 1 1 d . . . . .
H14A H 0.297661 0.599235 0.553656 0.015 Uiso 1 1 calc R U . . .
C15 C 0.45105(16) 0.64902(14) 0.43137(12) 0.0096(2) Uani 1 1 d . . . . .
C21 C 0.58443(17) 0.69345(14) 0.51046(12) 0.0100(2) Uani 1 1 d . . . . .
C22 C 0.58005(17) 0.69969(15) 0.63215(12) 0.0113(2) Uani 1 1 d . . . . .
H22A H 0.487678 0.678246 0.669561 0.014 Uiso 1 1 calc R U . . .
C23 C 0.71392(17) 0.73803(15) 0.69776(12) 0.0113(2) Uani 1 1 d . . . . .
C24 C 0.84636(17) 0.77186(15) 0.64020(12) 0.0118(2) Uani 1 1 d . . . . .
H24A H 0.939381 0.795895 0.683168 0.014 Uiso 1 1 calc R U . . .
C25 C 0.84073(16) 0.77002(14) 0.51873(12) 0.0098(2) Uani 1 1 d . . . . .
C31 C 1.05134(18) 0.85640(17) 0.26449(13) 0.0149(3) Uani 1 1 d . . . . .
H31A H 1.030752 0.853735 0.182692 0.018 Uiso 1 1 calc R U . . .
C32 C 1.19426(18) 0.90637(16) 0.30803(14) 0.0158(3) Uani 1 1 d . . . . .
H32A H 1.270258 0.935908 0.257112 0.019 Uiso 1 1 calc R U . . .
C33 C 1.22373(18) 0.91226(16) 0.42737(14) 0.0146(3) Uani 1 1 d . . . . .
H33A H 1.320334 0.946546 0.460023 0.017 Uiso 1 1 calc R U . . .
C34 C 1.10976(18) 0.86722(15) 0.49863(13) 0.0131(3) Uani 1 1 d . . . . .
H34A H 1.127266 0.870899 0.580849 0.016 Uiso 1 1 calc R U . . .
C35 C 0.97012(17) 0.81683(14) 0.44851(12) 0.0104(2) Uani 1 1 d . . . . .
C41 C 0.59470(19) 0.78081(18) 1.01034(13) 0.0163(3) Uani 1 1 d . . . . .
H41A H 0.511423 0.812131 1.052563 0.020 Uiso 1 1 calc R U . . .
C42 C 0.59060(19) 0.78182(17) 0.88973(13) 0.0155(3) Uani 1 1 d . . . . .
H42A H 0.504485 0.809966 0.850402 0.019 Uiso 1 1 calc R U . . .
C43 C 0.71435(17) 0.74105(15) 0.82697(12) 0.0119(2) Uani 1 1 d . . . . .
C44 C 0.83751(18) 0.70050(16) 0.88957(13) 0.0135(3) Uani 1 1 d . . . . .
H44A H 0.925766 0.675254 0.850299 0.016 Uiso 1 1 calc R U . . .
C45 C 0.82947(18) 0.69754(17) 1.00956(13) 0.0142(3) Uani 1 1 d . . . . .
H45A H 0.911767 0.665630 1.050689 0.017 Uiso 1 1 calc R U . . .
O1 O 1.20389(18) 0.73758(18) 1.00822(13) 0.0309(3) Uani 1 1 d . . . . .
H1 H 1.208(4) 0.679(3) 0.957(3) 0.053(10) Uiso 1 1 d . . . . .
C51 C 1.1996(3) 0.8624(3) 0.9650(2) 0.0363(5) Uani 1 1 d . . . . .
H51C H 1.096754 0.891881 0.972164 0.054 Uiso 1 1 calc R U . . .
H51A H 1.226740 0.855976 0.882609 0.054 Uiso 1 1 calc R U . . .
H51B H 1.272307 0.925724 1.010357 0.054 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 N2 2.2147(12) . ?
Mn1 N4 2.2301(12) 1_554 ?
Mn1 N1 2.2457(13) . ?
Mn1 N3 2.2577(13) . ?
Mn1 Br1 2.6563(3) . ?
Mn1 Br2 2.7714(3) . ?
N1 C11 1.3389(19) . ?
N1 C15 1.3548(18) . ?
N2 C21 1.3403(19) . ?
N2 C25 1.3412(18) . ?
N3 C31 1.337(2) . ?
N3 C35 1.3529(18) . ?
N4 C45 1.343(2) . ?
N4 C41 1.345(2) . ?
C11 C12 1.386(2) . ?
C11 H11A 0.9500 . ?
C12 C13 1.383(2) . ?
C12 H12A 0.9500 . ?
C13 C14 1.386(2) . ?
C13 H13A 0.9500 . ?
C14 C15 1.390(2) . ?
C14 H14A 0.9500 . ?
C15 C21 1.484(2) . ?
C21 C22 1.3952(19) . ?
C22 C23 1.394(2) . ?
C22 H22A 0.9500 . ?
C23 C24 1.392(2) . ?
C23 C43 1.4816(19) . ?
C24 C25 1.3933(19) . ?
C24 H24A 0.9500 . ?
C25 C35 1.487(2) . ?
C31 C32 1.386(2) . ?
C31 H31A 0.9500 . ?
C32 C33 1.384(2) . ?
C32 H32A 0.9500 . ?
C33 C34 1.389(2) . ?
C33 H33A 0.9500 . ?
C34 C35 1.387(2) . ?
C34 H34A 0.9500 . ?
C41 C42 1.386(2) . ?
C41 H41A 0.9500 . ?
C42 C43 1.392(2) . ?
C42 H42A 0.9500 . ?
C43 C44 1.397(2) . ?
C44 C45 1.385(2) . ?
C44 H44A 0.9500 . ?
C45 H45A 0.9500 . ?
O1 C51 1.414(3) . ?
O1 H1 0.81(4) . ?
C51 H51C 0.9800 . ?
C51 H51A 0.9800 . ?
C51 H51B 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N2 Mn1 N4 177.13(5) . 1_554 ?
N2 Mn1 N1 72.41(5) . . ?
N4 Mn1 N1 110.03(5) 1_554 . ?
N2 Mn1 N3 72.12(4) . . ?
N4 Mn1 N3 105.44(5) 1_554 . ?
N1 Mn1 N3 144.53(4) . . ?
N2 Mn1 Br1 91.68(3) . . ?
N4 Mn1 Br1 89.88(4) 1_554 . ?
N1 Mn1 Br1 89.30(4) . . ?
N3 Mn1 Br1 91.68(4) . . ?
N2 Mn1 Br2 91.53(3) . . ?
N4 Mn1 Br2 87.00(4) 1_554 . ?
N1 Mn1 Br2 89.71(4) . . ?
N3 Mn1 Br2 91.27(4) . . ?
Br1 Mn1 Br2 176.180(10) . . ?
C11 N1 C15 118.23(13) . . ?
C11 N1 Mn1 124.09(10) . . ?
C15 N1 Mn1 117.51(10) . . ?
C21 N2 C25 120.62(12) . . ?
C21 N2 Mn1 119.32(9) . . ?
C25 N2 Mn1 119.93(9) . . ?
C31 N3 C35 118.26(13) . . ?
C31 N3 Mn1 124.07(10) . . ?
C35 N3 Mn1 117.64(10) . . ?
C45 N4 C41 117.46(13) . . ?
C45 N4 Mn1 121.68(10) . 1_556 ?
C41 N4 Mn1 120.86(10) . 1_556 ?
N1 C11 C12 123.07(14) . . ?
N1 C11 H11A 118.5 . . ?
C12 C11 H11A 118.5 . . ?
C13 C12 C11 118.44(14) . . ?
C13 C12 H12A 120.8 . . ?
C11 C12 H12A 120.8 . . ?
C12 C13 C14 119.38(14) . . ?
C12 C13 H13A 120.3 . . ?
C14 C13 H13A 120.3 . . ?
C13 C14 C15 118.87(14) . . ?
C13 C14 H14A 120.6 . . ?
C15 C14 H14A 120.6 . . ?
N1 C15 C14 121.93(13) . . ?
N1 C15 C21 115.45(12) . . ?
C14 C15 C21 122.62(13) . . ?
N2 C21 C22 121.32(13) . . ?
N2 C21 C15 115.07(12) . . ?
C22 C21 C15 123.60(13) . . ?
C23 C22 C21 118.68(13) . . ?
C23 C22 H22A 120.7 . . ?
C21 C22 H22A 120.7 . . ?
C24 C23 C22 119.14(13) . . ?
C24 C23 C43 120.85(13) . . ?
C22 C23 C43 120.01(13) . . ?
C23 C24 C25 119.13(13) . . ?
C23 C24 H24A 120.4 . . ?
C25 C24 H24A 120.4 . . ?
N2 C25 C24 120.98(13) . . ?
N2 C25 C35 114.88(12) . . ?
C24 C25 C35 124.09(13) . . ?
N3 C31 C32 123.24(14) . . ?
N3 C31 H31A 118.4 . . ?
C32 C31 H31A 118.4 . . ?
C33 C32 C31 118.48(14) . . ?
C33 C32 H32A 120.8 . . ?
C31 C32 H32A 120.8 . . ?
C32 C33 C34 118.91(14) . . ?
C32 C33 H33A 120.5 . . ?
C34 C33 H33A 120.5 . . ?
C35 C34 C33 119.33(14) . . ?
C35 C34 H34A 120.3 . . ?
C33 C34 H34A 120.3 . . ?
N3 C35 C34 121.76(14) . . ?
N3 C35 C25 115.44(12) . . ?
C34 C35 C25 122.75(13) . . ?
N4 C41 C42 123.20(15) . . ?
N4 C41 H41A 118.4 . . ?
C42 C41 H41A 118.4 . . ?
C41 C42 C43 119.12(15) . . ?
C41 C42 H42A 120.4 . . ?
C43 C42 H42A 120.4 . . ?
C42 C43 C44 117.83(13) . . ?
C42 C43 C23 121.06(14) . . ?
C44 C43 C23 121.10(14) . . ?
C45 C44 C43 119.21(14) . . ?
C45 C44 H44A 120.4 . . ?
C43 C44 H44A 120.4 . . ?
N4 C45 C44 123.08(15) . . ?
N4 C45 H45A 118.5 . . ?
C44 C45 H45A 118.5 . . ?
C51 O1 H1 112(2) . . ?
O1 C51 H51C 109.5 . . ?
O1 C51 H51A 109.5 . . ?
H51C C51 H51A 109.5 . . ?
O1 C51 H51B 109.5 . . ?
H51C C51 H51B 109.5 . . ?
H51A C51 H51B 109.5 . . ?

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
C15 N1 C11 C12 0.3(2) . . . . ?
Mn1 N1 C11 C12 -174.94(12) . . . . ?
N1 C11 C12 C13 -2.6(3) . . . . ?
C11 C12 C13 C14 2.4(2) . . . . ?
C12 C13 C14 C15 0.0(2) . . . . ?
C11 N1 C15 C14 2.2(2) . . . . ?
Mn1 N1 C15 C14 177.77(11) . . . . ?
C11 N1 C15 C21 -177.45(14) . . . . ?
Mn1 N1 C15 C21 -1.87(17) . . . . ?
C13 C14 C15 N1 -2.3(2) . . . . ?
C13 C14 C15 C21 177.28(14) . . . . ?
C25 N2 C21 C22 1.4(2) . . . . ?
Mn1 N2 C21 C22 -174.40(11) . . . . ?
C25 N2 C21 C15 -179.27(13) . . . . ?
Mn1 N2 C21 C15 4.95(17) . . . . ?
N1 C15 C21 N2 -1.93(19) . . . . ?
C14 C15 C21 N2 178.43(14) . . . . ?
N1 C15 C21 C22 177.40(14) . . . . ?
C14 C15 C21 C22 -2.2(2) . . . . ?
N2 C21 C22 C23 -3.2(2) . . . . ?
C15 C21 C22 C23 177.50(14) . . . . ?
C21 C22 C23 C24 1.6(2) . . . . ?
C21 C22 C23 C43 -177.81(14) . . . . ?
C22 C23 C24 C25 1.8(2) . . . . ?
C43 C23 C24 C25 -178.89(14) . . . . ?
C21 N2 C25 C24 2.1(2) . . . . ?
Mn1 N2 C25 C24 177.86(11) . . . . ?
C21 N2 C25 C35 -175.39(13) . . . . ?
Mn1 N2 C25 C35 0.37(17) . . . . ?
C23 C24 C25 N2 -3.7(2) . . . . ?
C23 C24 C25 C35 173.59(14) . . . . ?
C35 N3 C31 C32 0.6(2) . . . . ?
Mn1 N3 C31 C32 178.43(13) . . . . ?
N3 C31 C32 C33 -1.0(3) . . . . ?
C31 C32 C33 C34 0.4(2) . . . . ?
C32 C33 C34 C35 0.4(2) . . . . ?
C31 N3 C35 C34 0.3(2) . . . . ?
Mn1 N3 C35 C34 -177.64(11) . . . . ?
C31 N3 C35 C25 177.91(14) . . . . ?
Mn1 N3 C35 C25 -0.02(17) . . . . ?
C33 C34 C35 N3 -0.8(2) . . . . ?
C33 C34 C35 C25 -178.27(14) . . . . ?
N2 C25 C35 N3 -0.2(2) . . . . ?
C24 C25 C35 N3 -177.63(14) . . . . ?
N2 C25 C35 C34 177.37(14) . . . . ?
C24 C25 C35 C34 0.0(2) . . . . ?
C45 N4 C41 C42 2.0(3) . . . . ?
Mn1 N4 C41 C42 -178.35(13) 1_556 . . . ?
N4 C41 C42 C43 -2.5(3) . . . . ?
C41 C42 C43 C44 0.1(2) . . . . ?
C41 C42 C43 C23 178.83(16) . . . . ?
C24 C23 C43 C42 142.97(16) . . . . ?
C22 C23 C43 C42 -37.7(2) . . . . ?
C24 C23 C43 C44 -38.4(2) . . . . ?
C22 C23 C43 C44 140.98(16) . . . . ?
C42 C43 C44 C45 2.5(2) . . . . ?
C23 C43 C44 C45 -176.22(15) . . . . ?
C41 N4 C45 C44 0.9(2) . . . . ?
Mn1 N4 C45 C44 -178.82(12) 1_556 . . . ?
C43 C44 C45 N4 -3.1(3) . . . . ?

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
O1 H1 Br2 0.81(4) 2.58(4) 3.3822(17) 170(3) 2_766 yes

_refine_diff_density_max         1.327
_refine_diff_density_min         -0.718
_refine_diff_density_rms         0.115

