# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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_lk-mn-br_auto
_database_code_depnum_ccdc_archive 'CCDC 2268961'
loop_
_audit_author_name
_audit_author_address
'Ling-Kun Wu'
;Jiangxi University of Science and Technology
China
;
_audit_update_record             
;
2023-06-10 deposited with the CCDC.	2023-07-24 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         ?
_chemical_formula_sum            'C14 H32 Br4 Mn N2'
_chemical_formula_weight         602.99

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'
Br Br -0.2901 2.4595 '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'

_space_group_crystal_system      tetragonal
_space_group_IT_number           113
_space_group_name_H-M_alt        'P -4 21 m'
_space_group_name_Hall           'P -4 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, -y, z'
'y, -x, -z'
'-y, x, -z'
'-x+1/2, y+1/2, -z'
'x+1/2, -y+1/2, -z'
'-y+1/2, -x+1/2, z'
'y+1/2, x+1/2, z'

_cell_length_a                   12.8275(5)
_cell_length_b                   12.8275(5)
_cell_length_c                   14.1940(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2335.5(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    3780
_cell_measurement_theta_min      2.1530
_cell_measurement_theta_max      27.2710
_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.715
_exptl_crystal_F_000             1180
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.14
_exptl_absorpt_coefficient_mu    7.406
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            10791
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_av_R_equivalents  0.0407
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.665
_diffrn_reflns_theta_max         28.731
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.883
_diffrn_measured_fraction_theta_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.883
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.843
_diffrn_reflns_point_group_measured_fraction_full 0.984
_reflns_number_total             2718
_reflns_number_gt                2313
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.706
_reflns_Friedel_fraction_max     0.793
_reflns_Friedel_fraction_full    0.981

_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0215P)²+2.4201P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.0010(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
;
 Flack x determined using 860 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(11)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2718
_refine_ls_number_parameters     129
_refine_ls_number_restraints     52
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0296
_refine_ls_wR_factor_ref         0.0641
_refine_ls_wR_factor_gt          0.0611
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_restrained_S_all      1.063
_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
Br1 Br 0.62101(4) 0.12101(4) 0.79277(7) 0.0346(2) Uani 1 2 d S T P . .
Br3 Br 0.74800(6) 0.24800(6) 0.55835(5) 0.0367(2) Uani 1 2 d S T P . .
Br2 Br 0.70608(5) 0.43202(4) 0.79091(4) 0.03848(18) Uani 1 1 d . . . . .
Mn1 Mn 0.75168(7) 0.25168(7) 0.73549(7) 0.0245(2) Uani 1 2 d S T P . .
N3 N 1.000000 0.500000 0.5155(8) 0.042(2) Uani 1 4 d S TU P . .
C8 C 0.8986(11) 0.3986(11) 0.3934(15) 0.064(6) Uani 0.5 2 d DS TU P . .
H8A H 0.844366 0.344366 0.400951 0.077 Uiso 1 2 calc R U P . .
H8B H 0.916456 0.416456 0.327447 0.077 Uiso 1 2 calc R U P . .
C9 C 0.9730(11) 0.4042(12) 0.4575(11) 0.058(4) Uani 0.5 1 d D U P . .
C10 C 0.9727(11) 0.5976(11) 0.5753(10) 0.049(3) Uani 0.5 1 d D U P . .
C11 C 0.9039(10) 0.5961(10) 0.6451(12) 0.048(5) Uani 0.5 2 d DS TU P . .
H11A H 0.927847 0.572153 0.707754 0.057 Uiso 1 2 calc R U P . .
H11B H 0.849364 0.650636 0.646023 0.057 Uiso 1 2 calc R U P . .
N1 N 0.8028(3) 0.3028(3) 0.0789(4) 0.0220(12) Uani 1 2 d S T P . .
C1 C 0.8715(5) 0.3715(5) 0.0222(6) 0.0322(18) Uani 1 2 d S T P . .
H1A H 0.925541 0.329391 -0.008338 0.048 Uiso 0.5 1 calc R U P A -1
H1B H 0.904264 0.423208 0.063451 0.048 Uiso 0.5 1 calc R U P A -1
H1C H 0.829963 0.407170 -0.025953 0.048 Uiso 0.5 1 calc R U P A -1
C2 C 0.7375(4) 0.2375(4) 0.0110(5) 0.0254(16) Uani 1 2 d S T P . .
H2A H 0.697171 0.285219 -0.029904 0.030 Uiso 0.5 1 calc R U P . .
H2B H 0.785219 0.197171 -0.029904 0.030 Uiso 0.5 1 calc R U P . .
C3 C 0.6627(4) 0.1627(4) 0.0579(6) 0.0319(18) Uani 1 2 d S T P . .
H3A H 0.640721 0.109652 0.012346 0.048 Uiso 0.5 1 calc R U P B -1
H3B H 0.601499 0.201047 0.080416 0.048 Uiso 0.5 1 calc R U P B -1
H3C H 0.697348 0.128868 0.111298 0.048 Uiso 0.5 1 calc R U P B -1
C4 C 0.7344(5) 0.3692(4) 0.1431(4) 0.0346(13) Uani 1 1 d . . . . .
H4A H 0.693222 0.322366 0.184198 0.041 Uiso 1 1 calc R U . . .
H4B H 0.779967 0.411758 0.184152 0.041 Uiso 1 1 calc R U . . .
C5 C 0.6598(5) 0.4416(5) 0.0911(5) 0.0404(15) Uani 1 1 d . . . . .
H5A H 0.699499 0.487473 0.049198 0.061 Uiso 1 1 calc R U . . .
H5B H 0.621119 0.483748 0.136853 0.061 Uiso 1 1 calc R U . . .
H5C H 0.610699 0.399991 0.053824 0.061 Uiso 1 1 calc R U . . .
N2 N 0.500000 0.500000 0.500000 0.031(2) Uani 1 4 d S T P . .
C6 C 0.6209(8) 0.4438(9) 0.3722(6) 0.082(3) Uani 1 1 d . . . . .
H6A H 0.590833 0.492793 0.326667 0.123 Uiso 1 1 calc R U . . .
H6B H 0.645672 0.381569 0.339011 0.123 Uiso 1 1 calc R U . . .
H6C H 0.679491 0.477143 0.404720 0.123 Uiso 1 1 calc R U . . .
C7 C 0.5434(5) 0.4147(5) 0.4394(4) 0.0393(15) Uani 1 1 d . . . . .
H7A H 0.573540 0.360831 0.481165 0.047 Uiso 1 1 calc R U . . .
H7B H 0.484724 0.382053 0.404934 0.047 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
Br1 Mn1 2.5060(14) . ?
Br3 Mn1 2.5153(12) . ?
Br2 Mn1 2.5124(9) . ?
N3 C9 1.519(14) 8_545 ?
N3 C9 1.519(14) . ?
N3 C9 1.519(14) 7_665 ?
N3 C9 1.519(14) 2_765 ?
N3 C10 1.552(15) 8_545 ?
N3 C10 1.552(15) . ?
N3 C10 1.552(15) 7_665 ?
N3 C10 1.552(15) 2_765 ?
C8 C9 1.321(18) . ?
C8 C9 1.321(18) 8_545 ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C9 C10 1.81(2) 2_765 ?
C10 C11 1.327(17) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
N1 C1 1.483(10) . ?
N1 C4 1.525(6) 8_545 ?
N1 C4 1.525(6) . ?
N1 C2 1.526(9) . ?
C1 H1A 0.9800 . ?
C1 H1B 0.9800 . ?
C1 H1C 0.9800 . ?
C2 C3 1.512(11) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 C5 1.524(9) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 H5A 0.9800 . ?
C5 H5B 0.9800 . ?
C5 H5C 0.9800 . ?
N2 C7 1.499(6) 4_656 ?
N2 C7 1.499(6) 3_566 ?
N2 C7 1.499(6) 2_665 ?
N2 C7 1.499(6) . ?
C6 C7 1.428(11) . ?
C6 H6A 0.9800 . ?
C6 H6B 0.9800 . ?
C6 H6C 0.9800 . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Br1 Mn1 Br2 111.01(3) . . ?
Br1 Mn1 Br2 111.01(3) . 8_545 ?
Br2 Mn1 Br2 109.32(5) . 8_545 ?
Br1 Mn1 Br3 107.41(5) . . ?
Br2 Mn1 Br3 109.02(3) . . ?
Br2 Mn1 Br3 109.02(3) 8_545 . ?
C9 N3 C9 48.5(12) 8_545 . ?
C9 N3 C9 114.3(15) 8_545 7_665 ?
C9 N3 C9 94.2(13) . 7_665 ?
C9 N3 C9 94.2(13) 8_545 2_765 ?
C9 N3 C9 114.3(15) . 2_765 ?
C9 N3 C9 48.5(12) 7_665 2_765 ?
C9 N3 C10 153.8(8) 8_545 8_545 ?
C9 N3 C10 107.3(8) . 8_545 ?
C9 N3 C10 72.3(9) 7_665 8_545 ?
C9 N3 C10 107.1(7) 2_765 8_545 ?
C9 N3 C10 107.3(8) 8_545 . ?
C9 N3 C10 153.8(8) . . ?
C9 N3 C10 107.1(7) 7_665 . ?
C9 N3 C10 72.3(9) 2_765 . ?
C10 N3 C10 93.8(12) 8_545 . ?
C9 N3 C10 72.3(9) 8_545 7_665 ?
C9 N3 C10 107.1(7) . 7_665 ?
C9 N3 C10 153.8(8) 7_665 7_665 ?
C9 N3 C10 107.3(8) 2_765 7_665 ?
C10 N3 C10 113.8(13) 8_545 7_665 ?
C10 N3 C10 48.6(10) . 7_665 ?
C9 N3 C10 107.2(7) 8_545 2_765 ?
C9 N3 C10 72.3(9) . 2_765 ?
C9 N3 C10 107.3(8) 7_665 2_765 ?
C9 N3 C10 153.8(8) 2_765 2_765 ?
C10 N3 C10 48.6(10) 8_545 2_765 ?
C10 N3 C10 113.8(13) . 2_765 ?
C10 N3 C10 93.8(12) 7_665 2_765 ?
C9 C8 C9 56.4(15) . 8_545 ?
C9 C8 H8A 118.1 . . ?
C9 C8 H8A 118.1 8_545 . ?
C9 C8 H8B 118.1 . . ?
C9 C8 H8B 118.1 8_545 . ?
H8A C8 H8B 115.3 . . ?
C8 C9 N3 125.6(13) . . ?
C8 C9 C10 155.9(16) . 2_765 ?
N3 C9 C10 54.7(7) . 2_765 ?
C11 C10 N3 123.0(11) . . ?
C10 C11 C10 57.5(13) 7_665 . ?
C10 C11 H11A 118.0 7_665 . ?
C10 C11 H11A 118.0 . . ?
C10 C11 H11B 118.0 7_665 . ?
C10 C11 H11B 118.0 . . ?
H11A C11 H11B 115.2 . . ?
C1 N1 C4 109.5(4) . 8_545 ?
C1 N1 C4 109.5(4) . . ?
C4 N1 C4 106.6(6) 8_545 . ?
C1 N1 C2 108.0(6) . . ?
C4 N1 C2 111.6(4) 8_545 . ?
C4 N1 C2 111.6(4) . . ?
N1 C1 H1A 109.5 . . ?
N1 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
N1 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
C3 C2 N1 114.8(6) . . ?
C3 C2 H2A 108.6 . . ?
N1 C2 H2A 108.6 . . ?
C3 C2 H2B 108.6 . . ?
N1 C2 H2B 108.6 . . ?
H2A C2 H2B 107.6 . . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
C5 C4 N1 114.4(5) . . ?
C5 C4 H4A 108.7 . . ?
N1 C4 H4A 108.7 . . ?
C5 C4 H4B 108.7 . . ?
N1 C4 H4B 108.7 . . ?
H4A C4 H4B 107.6 . . ?
C4 C5 H5A 109.5 . . ?
C4 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
C4 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
C7 N2 C7 109.9(5) 4_656 3_566 ?
C7 N2 C7 109.3(3) 4_656 2_665 ?
C7 N2 C7 109.3(3) 3_566 2_665 ?
C7 N2 C7 109.3(3) 4_656 . ?
C7 N2 C7 109.3(3) 3_566 . ?
C7 N2 C7 109.9(5) 2_665 . ?
C7 C6 H6A 109.5 . . ?
C7 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
C7 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
C6 C7 N2 116.8(6) . . ?
C6 C7 H7A 108.1 . . ?
N2 C7 H7A 108.1 . . ?
C6 C7 H7B 108.1 . . ?
N2 C7 H7B 108.1 . . ?
H7A C7 H7B 107.3 . . ?

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
C9 C8 C9 N3 -17(2) 8_545 . . . ?
C9 C8 C9 C10 65(3) 8_545 . . 2_765 ?
C9 N3 C9 C8 16(2) 8_545 . . . ?
C9 N3 C9 C8 -102.8(18) 7_665 . . . ?
C9 N3 C9 C8 -56.9(17) 2_765 . . . ?
C10 N3 C9 C8 -175.6(17) 8_545 . . . ?
C10 N3 C9 C8 42(4) . . . . ?
C10 N3 C9 C8 62(2) 7_665 . . . ?
C10 N3 C9 C8 150(2) 2_765 . . . ?
C9 N3 C9 C10 -134.1(7) 8_545 . . 2_765 ?
C9 N3 C9 C10 106.8(9) 7_665 . . 2_765 ?
C9 N3 C9 C10 152.8(8) 2_765 . . 2_765 ?
C10 N3 C9 C10 34.1(9) 8_545 . . 2_765 ?
C10 N3 C9 C10 -108(3) . . . 2_765 ?
C10 N3 C9 C10 -88.5(13) 7_665 . . 2_765 ?
C9 N3 C10 C11 68.1(19) 8_545 . . . ?
C9 N3 C10 C11 48(3) . . . . ?
C9 N3 C10 C11 -168.7(16) 7_665 . . . ?
C9 N3 C10 C11 157.0(18) 2_765 . . . ?
C10 N3 C10 C11 -96.2(16) 8_545 . . . ?
C10 N3 C10 C11 22.6(18) 7_665 . . . ?
C10 N3 C10 C11 -50.3(14) 2_765 . . . ?
N3 C10 C11 C10 -23.6(18) . . . 7_665 ?
C1 N1 C2 C3 180.000(0) . . . . ?
C4 N1 C2 C3 59.6(4) 8_545 . . . ?
C4 N1 C2 C3 -59.6(4) . . . . ?
C1 N1 C4 C5 63.0(7) . . . . ?
C4 N1 C4 C5 -178.6(3) 8_545 . . . ?
C2 N1 C4 C5 -56.5(7) . . . . ?
C7 N2 C7 C6 -63.9(5) 4_656 . . . ?
C7 N2 C7 C6 175.9(7) 3_566 . . . ?
C7 N2 C7 C6 56.0(6) 2_665 . . . ?

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
C8 H8B Br1 0.99 3.17 3.896(19) 131.7 4_656 yes
C8 H8B Br1 0.99 3.17 3.896(19) 131.7 3_666 yes
C8 H8A Br3 0.99 2.84 3.60(2) 134.3 . yes
C3 H3A^a Br1 0.98 3.13 3.838(9) 130.4 1_554 yes
C4 H4B Br1 0.99 2.99 3.835(6) 144.2 4_656 yes
C7 H7A Br3 0.99 2.88 3.784(6) 151.9 . yes
C7 H7B Br2 0.99 3.08 3.889(6) 140.2 3_566 yes

_refine_diff_density_max         0.602
_refine_diff_density_min         -0.618
_refine_diff_density_rms         0.082

