# Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers.
# This journal is © the Partner Organisations 2022

####################################################################### 
# 
# 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_AJ121
_database_code_depnum_ccdc_archive 'CCDC 1896736'
loop_
_audit_author_name
_audit_author_address
'ATANU JANA'
;Ulsan National Institute of Science and Technology
South Korea
;
_audit_update_record             
;
2019-02-12 deposited with the CCDC.	2022-08-30 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C9 H14 N, Br'
_chemical_formula_sum            'C9 H14 Br N'
_chemical_formula_weight         216.12

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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_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'

_cell_length_a                   6.8492(4)
_cell_length_b                   10.7579(7)
_cell_length_c                   13.7900(8)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1016.09(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    9945
_cell_measurement_theta_min      2.40
_cell_measurement_theta_max      28.13

_exptl_crystal_description       Block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.413
_exptl_crystal_F_000             440
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.110
_exptl_absorpt_coefficient_mu    3.989
_shelx_estimated_absorpt_T_min   0.488
_shelx_estimated_absorpt_T_max   0.668
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.5090
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   'Bruker SADABS'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'PHOTON 100 CMOS'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            29778
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.401
_diffrn_reflns_theta_max         28.325
_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 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2522
_reflns_number_gt                2245
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.710
_reflns_Friedel_fraction_max     0.995
_reflns_Friedel_fraction_full    0.996

_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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0294P)²+0.0923P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
; 
 Flack x determined using 869 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.000(5)
_chemical_absolute_configuration ab
_refine_ls_number_reflns         2522
_refine_ls_number_parameters     103
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0300
_refine_ls_R_factor_gt           0.0225
_refine_ls_wR_factor_ref         0.0566
_refine_ls_wR_factor_gt          0.0524
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_restrained_S_all      1.076
_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
N1 N 0.3451(4) 0.0829(2) 0.61441(16) 0.0408(5) Uani 1 1 d . . . . .
C1 C 0.1515(5) 0.0268(3) 0.5869(3) 0.0582(8) Uani 1 1 d . . . . .
H1A H 0.1411 0.0230 0.5175 0.087 Uiso 1 1 calc R U . . .
H1B H 0.0478 0.0772 0.6124 0.087 Uiso 1 1 calc R U . . .
H1C H 0.1421 -0.0555 0.6133 0.087 Uiso 1 1 calc R U . . .
C2 C 0.3598(5) 0.2133(3) 0.5752(2) 0.0508(7) Uani 1 1 d . . . . .
H2A H 0.4839 0.2482 0.5928 0.076 Uiso 1 1 calc R U . . .
H2B H 0.2570 0.2632 0.6021 0.076 Uiso 1 1 calc R U . . .
H2C H 0.3480 0.2115 0.5059 0.076 Uiso 1 1 calc R U . . .
C3 C 0.3502(6) 0.0924(3) 0.7235(2) 0.0567(8) Uani 1 1 d . . . . .
H3A H 0.3347 0.0111 0.7512 0.085 Uiso 1 1 calc R U . . .
H3B H 0.2461 0.1453 0.7451 0.085 Uiso 1 1 calc R U . . .
H3C H 0.4731 0.1268 0.7435 0.085 Uiso 1 1 calc R U . . .
C4 C 0.5034(4) 0.0015(3) 0.5743(2) 0.0384(5) Uani 1 1 d . . . . .
C5 C 0.5234(5) -0.0041(3) 0.4748(2) 0.0492(7) Uani 1 1 d . . . . .
H5 H 0.4464 0.0458 0.4351 0.059 Uiso 1 1 calc R U . . .
C6 C 0.6588(6) -0.0842(3) 0.4344(2) 0.0606(8) Uani 1 1 d . . . . .
H6 H 0.6719 -0.0888 0.3674 0.073 Uiso 1 1 calc R U . . .
C7 C 0.7741(5) -0.1572(3) 0.4931(3) 0.0598(9) Uani 1 1 d . . . . .
H7 H 0.8640 -0.2118 0.4659 0.072 Uiso 1 1 calc R U . . .
C8 C 0.7557(5) -0.1490(3) 0.5918(3) 0.0600(9) Uani 1 1 d . . . . .
H8 H 0.8356 -0.1971 0.6314 0.072 Uiso 1 1 calc R U . . .
C9 C 0.6201(4) -0.0702(3) 0.6332(2) 0.0497(7) Uani 1 1 d . . . . .
H9 H 0.6077 -0.0657 0.7003 0.060 Uiso 1 1 calc R U . . .
Br1 Br 0.83816(4) 0.27560(3) 0.70689(2) 0.04946(10) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
N1 C4 1.499(4) . ?
N1 C1 1.505(4) . ?
N1 C2 1.507(4) . ?
N1 C3 1.508(4) . ?
C1 H1A 0.9600 . ?
C1 H1B 0.9600 . ?
C1 H1C 0.9600 . ?
C2 H2A 0.9600 . ?
C2 H2B 0.9600 . ?
C2 H2C 0.9600 . ?
C3 H3A 0.9600 . ?
C3 H3B 0.9600 . ?
C3 H3C 0.9600 . ?
C4 C9 1.377(4) . ?
C4 C5 1.380(4) . ?
C5 C6 1.383(4) . ?
C5 H5 0.9300 . ?
C6 C7 1.376(5) . ?
C6 H6 0.9300 . ?
C7 C8 1.370(5) . ?
C7 H7 0.9300 . ?
C8 C9 1.381(5) . ?
C8 H8 0.9300 . ?
C9 H9 0.9300 . ?

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
C4 N1 C1 108.1(2) . . ?
C4 N1 C2 111.3(2) . . ?
C1 N1 C2 110.0(2) . . ?
C4 N1 C3 113.0(2) . . ?
C1 N1 C3 107.4(2) . . ?
C2 N1 C3 107.0(2) . . ?
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 . . ?
N1 C2 H2A 109.5 . . ?
N1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
N1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
N1 C3 H3A 109.5 . . ?
N1 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
N1 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
C9 C4 C5 120.3(3) . . ?
C9 C4 N1 122.0(3) . . ?
C5 C4 N1 117.7(3) . . ?
C4 C5 C6 119.6(3) . . ?
C4 C5 H5 120.2 . . ?
C6 C5 H5 120.2 . . ?
C7 C6 C5 120.2(3) . . ?
C7 C6 H6 119.9 . . ?
C5 C6 H6 119.9 . . ?
C8 C7 C6 119.7(3) . . ?
C8 C7 H7 120.2 . . ?
C6 C7 H7 120.2 . . ?
C7 C8 C9 120.8(3) . . ?
C7 C8 H8 119.6 . . ?
C9 C8 H8 119.6 . . ?
C4 C9 C8 119.4(3) . . ?
C4 C9 H9 120.3 . . ?
C8 C9 H9 120.3 . . ?

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
C1 N1 C4 C9 -109.6(3) . . . . ?
C2 N1 C4 C9 129.5(3) . . . . ?
C3 N1 C4 C9 9.1(4) . . . . ?
C1 N1 C4 C5 67.3(3) . . . . ?
C2 N1 C4 C5 -53.5(4) . . . . ?
C3 N1 C4 C5 -174.0(3) . . . . ?
C9 C4 C5 C6 1.3(5) . . . . ?
N1 C4 C5 C6 -175.7(3) . . . . ?
C4 C5 C6 C7 -0.6(5) . . . . ?
C5 C6 C7 C8 -0.7(5) . . . . ?
C6 C7 C8 C9 1.3(5) . . . . ?
C5 C4 C9 C8 -0.8(5) . . . . ?
N1 C4 C9 C8 176.1(3) . . . . ?
C7 C8 C9 C4 -0.6(5) . . . . ?

_refine_diff_density_max         0.401
_refine_diff_density_min         -0.169
_refine_diff_density_rms         0.051

####################################################################### 
# 
# 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_AJ115
_database_code_depnum_ccdc_archive 'CCDC 1896737'
loop_
_audit_author_name
_audit_author_address
'ATANU JANA'
;Ulsan National Institute of Science and Technology
South Korea
;
_audit_update_record             
;
2019-02-12 deposited with the CCDC.	2022-08-30 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         '2(C9 H14 N), Br4 Mn'
_chemical_formula_sum            'C18 H28 Br4 Mn N2'
_chemical_formula_weight         647.00

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'
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      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 2yc'

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

_cell_length_a                   17.1271(9)
_cell_length_b                   9.1787(5)
_cell_length_c                   47.166(3)
_cell_angle_alpha                90
_cell_angle_beta                 92.605(2)
_cell_angle_gamma                90
_cell_volume                     7407.1(7)
_cell_formula_units_Z            12
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    9942
_cell_measurement_theta_min      2.38
_cell_measurement_theta_max      24.92

_exptl_crystal_description       Block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.741
_exptl_crystal_F_000             3780
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    7.012
_shelx_estimated_absorpt_T_min   0.308
_shelx_estimated_absorpt_T_max   0.487
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.5415
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   'Bruker SADABS'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'PHOTON 100 CMOS'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            116783
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_av_R_equivalents  0.0673
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -62
_diffrn_reflns_limit_l_max       62
_diffrn_reflns_theta_min         2.381
_diffrn_reflns_theta_max         28.380
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             9231
_reflns_number_gt                6293
_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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_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)+(0.0275P)²+22.0464P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         9231
_refine_ls_number_parameters     348
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0438
_refine_ls_wR_factor_ref         0.0937
_refine_ls_wR_factor_gt          0.0833
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_restrained_S_all      1.078
_refine_ls_shift/su_max          0.003
_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 0.0000 0.52748(9) 0.7500 0.04376(19) Uani 1 2 d S T P . .
Br1 Br 0.08373(3) 0.69709(5) 0.72280(2) 0.05764(12) Uani 1 1 d . . . . .
Br2 Br 0.07531(3) 0.36703(5) 0.78416(2) 0.06432(13) Uani 1 1 d . . . . .
Mn2 Mn 0.72262(4) 0.59576(6) 0.91363(2) 0.04967(15) Uani 1 1 d . . . . .
Br3 Br 0.65782(3) 0.38448(6) 0.88884(2) 0.08081(17) Uani 1 1 d . . . . .
Br4 Br 0.78592(3) 0.74927(5) 0.87756(2) 0.06376(13) Uani 1 1 d . . . . .
Br5 Br 0.62996(3) 0.75528(6) 0.93879(2) 0.06821(14) Uani 1 1 d . . . . .
Br6 Br 0.82392(3) 0.50843(6) 0.94928(2) 0.07059(14) Uani 1 1 d . . . . .
N1 N 0.8314(3) 0.0294(5) 0.97061(9) 0.0841(13) Uani 1 1 d . . . . .
C1 C 0.8171(4) -0.1150(6) 0.98275(15) 0.114(2) Uani 1 1 d . . . . .
H1A H 0.7822 -0.1688 0.9702 0.170 Uiso 1 1 calc R U . . .
H1B H 0.7940 -0.1039 1.0008 0.170 Uiso 1 1 calc R U . . .
H1C H 0.8657 -0.1665 0.9852 0.170 Uiso 1 1 calc R U . . .
C2 C 0.7544(5) 0.1022(8) 0.9667(2) 0.202(6) Uani 1 1 d . . . . .
H2A H 0.7449 0.1608 0.9830 0.303 Uiso 1 1 calc R U . . .
H2B H 0.7141 0.0298 0.9644 0.303 Uiso 1 1 calc R U . . .
H2C H 0.7542 0.1630 0.9501 0.303 Uiso 1 1 calc R U . . .
C3 C 0.8608(6) 0.0086(12) 0.9427(2) 0.187(4) Uani 1 1 d . U . . .
H3A H 0.8683 0.1016 0.9339 0.280 Uiso 1 1 calc R U . . .
H3B H 0.8239 -0.0474 0.9313 0.280 Uiso 1 1 calc R U . . .
H3C H 0.9098 -0.0424 0.9443 0.280 Uiso 1 1 calc R U . . .
C4 C 0.8852(3) 0.1200(5) 0.98895(9) 0.0599(11) Uani 1 1 d . . . . .
C5 C 0.8763(4) 0.1159(7) 1.01739(11) 0.103(2) Uani 1 1 d . . . . .
H5 H 0.8398 0.0536 1.0249 0.123 Uiso 1 1 calc R U . . .
C6 C 0.9210(4) 0.2029(9) 1.03480(12) 0.118(3) Uani 1 1 d . . . . .
H6 H 0.9145 0.2007 1.0543 0.141 Uiso 1 1 calc R U . . .
C7 C 0.9744(3) 0.2921(8) 1.02424(14) 0.099(2) Uani 1 1 d . . . . .
H7 H 1.0045 0.3517 1.0364 0.119 Uiso 1 1 calc R U . . .
C8 C 0.9845(3) 0.2956(6) 0.99640(14) 0.0856(16) Uani 1 1 d . . . . .
H8 H 1.0219 0.3571 0.9892 0.103 Uiso 1 1 calc R U . . .
C9 C 0.9402(3) 0.2095(6) 0.97844(11) 0.0729(13) Uani 1 1 d . . . . .
H9 H 0.9475 0.2119 0.9590 0.087 Uiso 1 1 calc R U . . .
N2 N 0.51952(19) 1.0009(3) 0.87154(7) 0.0483(8) Uani 1 1 d . . . . .
C10 C 0.6045(2) 0.9864(5) 0.86729(10) 0.0637(12) Uani 1 1 d . . . . .
H10A H 0.6281 0.9284 0.8823 0.096 Uiso 1 1 calc R U . . .
H10B H 0.6281 1.0812 0.8674 0.096 Uiso 1 1 calc R U . . .
H10C H 0.6122 0.9401 0.8494 0.096 Uiso 1 1 calc R U . . .
C11 C 0.5094(3) 1.0713(5) 0.89999(9) 0.0660(12) Uani 1 1 d . . . . .
H11A H 0.5306 1.0087 0.9147 0.099 Uiso 1 1 calc R U . . .
H11B H 0.4548 1.0871 0.9027 0.099 Uiso 1 1 calc R U . . .
H11C H 0.5364 1.1630 0.9007 0.099 Uiso 1 1 calc R U . . .
C12 C 0.4858(3) 1.0971(5) 0.84828(10) 0.0704(13) Uani 1 1 d . . . . .
H12A H 0.5124 1.1892 0.8488 0.106 Uiso 1 1 calc R U . . .
H12B H 0.4312 1.1124 0.8510 0.106 Uiso 1 1 calc R U . . .
H12C H 0.4922 1.0513 0.8302 0.106 Uiso 1 1 calc R U . . .
C13 C 0.4780(2) 0.8567(4) 0.87087(8) 0.0501(10) Uani 1 1 d . . . . .
C14 C 0.3989(3) 0.8571(5) 0.87414(10) 0.0669(12) Uani 1 1 d . . . . .
H14 H 0.3721 0.9443 0.8763 0.080 Uiso 1 1 calc R U . . .
C15 C 0.3598(4) 0.7265(8) 0.87420(12) 0.0898(18) Uani 1 1 d . . . . .
H15 H 0.3060 0.7254 0.8761 0.108 Uiso 1 1 calc R U . . .
C16 C 0.3988(5) 0.5998(7) 0.87147(12) 0.097(2) Uani 1 1 d . . . . .
H16 H 0.3720 0.5117 0.8718 0.116 Uiso 1 1 calc R U . . .
C17 C 0.4770(4) 0.6010(6) 0.86822(12) 0.0917(19) Uani 1 1 d . . . . .
H17 H 0.5033 0.5133 0.8661 0.110 Uiso 1 1 calc R U . . .
C18 C 0.5184(3) 0.7301(5) 0.86795(10) 0.0682(13) Uani 1 1 d . . . . .
H18 H 0.5721 0.7306 0.8658 0.082 Uiso 1 1 calc R U . . .
N3 N 0.6949(2) 0.4489(4) 0.79404(7) 0.0531(8) Uani 1 1 d . . . . .
C19 C 0.6103(3) 0.4248(6) 0.79806(12) 0.0788(14) Uani 1 1 d . . . . .
H19A H 0.5897 0.3587 0.7838 0.118 Uiso 1 1 calc R U . . .
H19B H 0.5830 0.5159 0.7964 0.118 Uiso 1 1 calc R U . . .
H19C H 0.6035 0.3840 0.8165 0.118 Uiso 1 1 calc R U . . .
C20 C 0.7034(3) 0.5068(5) 0.76426(9) 0.0743(14) Uani 1 1 d . . . . .
H20A H 0.6844 0.4355 0.7507 0.111 Uiso 1 1 calc R U . . .
H20B H 0.7575 0.5267 0.7613 0.111 Uiso 1 1 calc R U . . .
H20C H 0.6736 0.5949 0.7618 0.111 Uiso 1 1 calc R U . . .
C21 C 0.7229(3) 0.5625(5) 0.81512(10) 0.0662(12) Uani 1 1 d . . . . .
H21A H 0.6896 0.6466 0.8134 0.099 Uiso 1 1 calc R U . . .
H21B H 0.7755 0.5899 0.8114 0.099 Uiso 1 1 calc R U . . .
H21C H 0.7213 0.5236 0.8340 0.099 Uiso 1 1 calc R U . . .
C22 C 0.7435(2) 0.3137(4) 0.79785(8) 0.0484(9) Uani 1 1 d . . . . .
C23 C 0.8227(3) 0.3245(5) 0.79518(9) 0.0624(12) Uani 1 1 d . . . . .
H23 H 0.8451 0.4139 0.7911 0.075 Uiso 1 1 calc R U . . .
C24 C 0.8686(3) 0.2032(6) 0.79854(11) 0.0739(13) Uani 1 1 d . . . . .
H24 H 0.9223 0.2100 0.7966 0.089 Uiso 1 1 calc R U . . .
C25 C 0.8357(3) 0.0712(6) 0.80485(10) 0.0723(13) Uani 1 1 d . . . . .
H25 H 0.8669 -0.0110 0.8074 0.087 Uiso 1 1 calc R U . . .
C26 C 0.7571(3) 0.0621(5) 0.80727(10) 0.0714(13) Uani 1 1 d . . . . .
H26 H 0.7349 -0.0274 0.8114 0.086 Uiso 1 1 calc R U . . .
C27 C 0.7096(3) 0.1824(5) 0.80371(9) 0.0611(11) Uani 1 1 d . . . . .
H27 H 0.6558 0.1747 0.8052 0.073 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 Br2 2.4979(6) . ?
Mn1 Br2 2.4980(6) 2_556 ?
Mn1 Br1 2.5086(6) 2_556 ?
Mn1 Br1 2.5087(6) . ?
Mn2 Br6 2.4928(8) . ?
Mn2 Br4 2.4946(7) . ?
Mn2 Br5 2.4982(8) . ?
Mn2 Br3 2.4984(8) . ?
N1 C3 1.443(10) . ?
N1 C1 1.468(7) . ?
N1 C2 1.484(9) . ?
N1 C4 1.488(6) . ?
C1 H1A 0.9600 . ?
C1 H1B 0.9600 . ?
C1 H1C 0.9600 . ?
C2 H2A 0.9600 . ?
C2 H2B 0.9600 . ?
C2 H2C 0.9600 . ?
C3 H3A 0.9600 . ?
C3 H3B 0.9600 . ?
C3 H3C 0.9600 . ?
C4 C5 1.357(6) . ?
C4 C9 1.360(7) . ?
C5 C6 1.356(8) . ?
C5 H5 0.9300 . ?
C6 C7 1.340(8) . ?
C6 H6 0.9300 . ?
C7 C8 1.333(8) . ?
C7 H7 0.9300 . ?
C8 C9 1.364(7) . ?
C8 H8 0.9300 . ?
C9 H9 0.9300 . ?
N2 C10 1.484(5) . ?
N2 C13 1.502(5) . ?
N2 C12 1.503(5) . ?
N2 C11 1.506(5) . ?
C10 H10A 0.9600 . ?
C10 H10B 0.9600 . ?
C10 H10C 0.9600 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?
C13 C18 1.363(6) . ?
C13 C14 1.371(6) . ?
C14 C15 1.373(7) . ?
C14 H14 0.9300 . ?
C15 C16 1.350(9) . ?
C15 H15 0.9300 . ?
C16 C17 1.355(9) . ?
C16 H16 0.9300 . ?
C17 C18 1.381(7) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
N3 C19 1.487(6) . ?
N3 C22 1.500(5) . ?
N3 C21 1.504(5) . ?
N3 C20 1.515(5) . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 C27 1.372(6) . ?
C22 C23 1.372(6) . ?
C23 C24 1.368(7) . ?
C23 H23 0.9300 . ?
C24 C25 1.374(7) . ?
C24 H24 0.9300 . ?
C25 C26 1.358(7) . ?
C25 H25 0.9300 . ?
C26 C27 1.377(7) . ?
C26 H26 0.9300 . ?
C27 H27 0.9300 . ?

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
Br2 Mn1 Br2 107.75(4) . 2_556 ?
Br2 Mn1 Br1 109.053(16) . 2_556 ?
Br2 Mn1 Br1 113.911(16) 2_556 2_556 ?
Br2 Mn1 Br1 113.910(16) . . ?
Br2 Mn1 Br1 109.049(16) 2_556 . ?
Br1 Mn1 Br1 103.28(3) 2_556 . ?
Br6 Mn2 Br4 109.32(3) . . ?
Br6 Mn2 Br5 107.81(3) . . ?
Br4 Mn2 Br5 107.34(3) . . ?
Br6 Mn2 Br3 110.29(3) . . ?
Br4 Mn2 Br3 108.47(3) . . ?
Br5 Mn2 Br3 113.51(3) . . ?
C3 N1 C1 107.9(6) . . ?
C3 N1 C2 106.9(6) . . ?
C1 N1 C2 106.9(6) . . ?
C3 N1 C4 111.9(6) . . ?
C1 N1 C4 112.8(4) . . ?
C2 N1 C4 110.1(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 . . ?
N1 C2 H2A 109.5 . . ?
N1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
N1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
N1 C3 H3A 109.5 . . ?
N1 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
N1 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
C5 C4 C9 119.2(5) . . ?
C5 C4 N1 117.7(4) . . ?
C9 C4 N1 123.1(4) . . ?
C6 C5 C4 119.8(5) . . ?
C6 C5 H5 120.1 . . ?
C4 C5 H5 120.1 . . ?
C7 C6 C5 120.7(5) . . ?
C7 C6 H6 119.7 . . ?
C5 C6 H6 119.7 . . ?
C8 C7 C6 120.1(6) . . ?
C8 C7 H7 119.9 . . ?
C6 C7 H7 119.9 . . ?
C7 C8 C9 120.3(5) . . ?
C7 C8 H8 119.9 . . ?
C9 C8 H8 119.9 . . ?
C4 C9 C8 119.9(5) . . ?
C4 C9 H9 120.0 . . ?
C8 C9 H9 120.0 . . ?
C10 N2 C13 112.6(3) . . ?
C10 N2 C12 107.5(3) . . ?
C13 N2 C12 109.7(3) . . ?
C10 N2 C11 108.2(3) . . ?
C13 N2 C11 108.9(3) . . ?
C12 N2 C11 110.0(3) . . ?
N2 C10 H10A 109.5 . . ?
N2 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
N2 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
N2 C11 H11A 109.5 . . ?
N2 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
N2 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
N2 C12 H12A 109.5 . . ?
N2 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
N2 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C18 C13 C14 121.5(4) . . ?
C18 C13 N2 120.8(4) . . ?
C14 C13 N2 117.7(4) . . ?
C13 C14 C15 118.9(5) . . ?
C13 C14 H14 120.6 . . ?
C15 C14 H14 120.6 . . ?
C16 C15 C14 120.5(6) . . ?
C16 C15 H15 119.7 . . ?
C14 C15 H15 119.7 . . ?
C15 C16 C17 119.9(5) . . ?
C15 C16 H16 120.0 . . ?
C17 C16 H16 120.0 . . ?
C16 C17 C18 121.3(6) . . ?
C16 C17 H17 119.4 . . ?
C18 C17 H17 119.4 . . ?
C13 C18 C17 117.9(5) . . ?
C13 C18 H18 121.1 . . ?
C17 C18 H18 121.1 . . ?
C19 N3 C22 113.5(3) . . ?
C19 N3 C21 107.6(4) . . ?
C22 N3 C21 109.7(3) . . ?
C19 N3 C20 107.8(4) . . ?
C22 N3 C20 109.0(3) . . ?
C21 N3 C20 109.2(3) . . ?
N3 C19 H19A 109.5 . . ?
N3 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
N3 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
N3 C20 H20A 109.5 . . ?
N3 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
N3 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
N3 C21 H21A 109.5 . . ?
N3 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
N3 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C27 C22 C23 120.8(4) . . ?
C27 C22 N3 120.9(4) . . ?
C23 C22 N3 118.3(4) . . ?
C24 C23 C22 119.8(4) . . ?
C24 C23 H23 120.1 . . ?
C22 C23 H23 120.1 . . ?
C23 C24 C25 120.2(5) . . ?
C23 C24 H24 119.9 . . ?
C25 C24 H24 119.9 . . ?
C26 C25 C24 119.4(5) . . ?
C26 C25 H25 120.3 . . ?
C24 C25 H25 120.3 . . ?
C25 C26 C27 121.5(5) . . ?
C25 C26 H26 119.2 . . ?
C27 C26 H26 119.2 . . ?
C22 C27 C26 118.4(4) . . ?
C22 C27 H27 120.8 . . ?
C26 C27 H27 120.8 . . ?

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
C3 N1 C4 C5 -162.6(7) . . . . ?
C1 N1 C4 C5 -40.7(7) . . . . ?
C2 N1 C4 C5 78.7(7) . . . . ?
C3 N1 C4 C9 19.8(8) . . . . ?
C1 N1 C4 C9 141.7(6) . . . . ?
C2 N1 C4 C9 -98.9(7) . . . . ?
C9 C4 C5 C6 1.5(10) . . . . ?
N1 C4 C5 C6 -176.2(6) . . . . ?
C4 C5 C6 C7 -0.7(12) . . . . ?
C5 C6 C7 C8 -0.4(12) . . . . ?
C6 C7 C8 C9 0.5(11) . . . . ?
C5 C4 C9 C8 -1.3(8) . . . . ?
N1 C4 C9 C8 176.3(5) . . . . ?
C7 C8 C9 C4 0.3(9) . . . . ?
C10 N2 C13 C18 2.9(5) . . . . ?
C12 N2 C13 C18 122.5(4) . . . . ?
C11 N2 C13 C18 -117.1(4) . . . . ?
C10 N2 C13 C14 -179.0(4) . . . . ?
C12 N2 C13 C14 -59.3(5) . . . . ?
C11 N2 C13 C14 61.1(5) . . . . ?
C18 C13 C14 C15 -0.6(7) . . . . ?
N2 C13 C14 C15 -178.7(4) . . . . ?
C13 C14 C15 C16 0.9(8) . . . . ?
C14 C15 C16 C17 -1.0(9) . . . . ?
C15 C16 C17 C18 0.7(9) . . . . ?
C14 C13 C18 C17 0.3(7) . . . . ?
N2 C13 C18 C17 178.4(4) . . . . ?
C16 C17 C18 C13 -0.4(8) . . . . ?
C19 N3 C22 C27 1.7(5) . . . . ?
C21 N3 C22 C27 122.0(4) . . . . ?
C20 N3 C22 C27 -118.5(4) . . . . ?
C19 N3 C22 C23 -178.7(4) . . . . ?
C21 N3 C22 C23 -58.4(5) . . . . ?
C20 N3 C22 C23 61.2(5) . . . . ?
C27 C22 C23 C24 -0.4(7) . . . . ?
N3 C22 C23 C24 180.0(4) . . . . ?
C22 C23 C24 C25 -0.6(7) . . . . ?
C23 C24 C25 C26 1.0(8) . . . . ?
C24 C25 C26 C27 -0.4(8) . . . . ?
C23 C22 C27 C26 1.0(6) . . . . ?
N3 C22 C27 C26 -179.4(4) . . . . ?
C25 C26 C27 C22 -0.6(7) . . . . ?

_refine_diff_density_max         0.753
_refine_diff_density_min         -0.481
_refine_diff_density_rms         0.083

