# Supplementary Information (SI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 2025

####################################################################### 
# 
# 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_1220
_database_code_depnum_ccdc_archive 'CCDC 2395302'
loop_
_audit_author_name
_audit_author_address
pmz-b
;Qingdao Agricultural University
China
;
_audit_update_record             
;
2024-11-01 deposited with the CCDC.	2025-01-02 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            'C20 H17 Br N2 O2'
_chemical_formula_weight         397.26

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'
O O 0.0106 0.0060 '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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   9.3775(13)
_cell_length_b                   9.8418(13)
_cell_length_c                   18.943(3)
_cell_angle_alpha                90
_cell_angle_beta                 96.999(5)
_cell_angle_gamma                90
_cell_volume                     1735.2(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    3042
_cell_measurement_theta_min      2.557
_cell_measurement_theta_max      25.020

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            YELLOW
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.521
_exptl_crystal_F_000             808
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.492
_exptl_crystal_size_mid          0.477
_exptl_crystal_size_min          0.425
_exptl_absorpt_coefficient_mu    2.385
_shelx_estimated_absorpt_T_min   0.387
_shelx_estimated_absorpt_T_max   0.431
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.387
_exptl_absorpt_correction_T_max  0.431
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      273(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   MoK\a
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            19651
_diffrn_reflns_av_unetI/netI     0.0182
_diffrn_reflns_av_R_equivalents  0.0238
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         2.557
_diffrn_reflns_theta_max         25.020
_diffrn_reflns_theta_full        25.020
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measured_fraction_theta_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.993
_reflns_number_total             3042
_reflns_number_gt                2566
_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    'SHELXL-2018/3 (Sheldrick, 2018)'
_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)+(0.0348P)²+0.7306P] 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         3042
_refine_ls_number_parameters     226
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0372
_refine_ls_R_factor_gt           0.0283
_refine_ls_wR_factor_ref         0.0732
_refine_ls_wR_factor_gt          0.0694
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_restrained_S_all      1.049
_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 0.13388(3) 1.04244(3) 0.40700(2) 0.06070(12) Uani 1 1 d . . . . .
N1 N 0.61310(19) 0.76119(19) 0.43837(9) 0.0474(4) Uani 1 1 d . . . . .
N2 N 0.5407(2) 0.77257(19) 0.21564(9) 0.0490(4) Uani 1 1 d . . . . .
O1 O 0.6524(2) 1.08496(18) 0.28096(10) 0.0739(5) Uani 1 1 d . . . . .
O2 O 0.60986(18) 0.90363(17) 0.21083(8) 0.0559(4) Uani 1 1 d . . . . .
C1 C 0.2622(2) 0.9107(2) 0.45311(11) 0.0430(5) Uani 1 1 d . . . . .
C2 C 0.2206(3) 0.8435(2) 0.51143(12) 0.0535(6) Uani 1 1 d . . . . .
H2 H 0.133644 0.863300 0.528043 0.064 Uiso 1 1 calc R U . . .
C3 C 0.3115(3) 0.7468(3) 0.54411(13) 0.0592(6) Uani 1 1 d . . . . .
H3 H 0.284761 0.699723 0.582997 0.071 Uiso 1 1 calc R U . . .
C4 C 0.4410(3) 0.7183(2) 0.52047(11) 0.0520(6) Uani 1 1 d . . . . .
H4 H 0.500418 0.651813 0.543149 0.062 Uiso 1 1 calc R U . . .
C5 C 0.4839(2) 0.7887(2) 0.46239(10) 0.0407(5) Uani 1 1 d . . . . .
C6 C 0.7124(3) 0.6561(3) 0.46526(15) 0.0656(7) Uani 1 1 d . . . . .
H6A H 0.671933 0.566760 0.454164 0.079 Uiso 1 1 calc R U . . .
H6B H 0.735938 0.663811 0.516400 0.079 Uiso 1 1 calc R U . . .
C7 C 0.8428(3) 0.6790(4) 0.42832(17) 0.0848(9) Uani 1 1 d . . . . .
H7A H 0.917650 0.723316 0.460030 0.102 Uiso 1 1 calc R U . . .
H7B H 0.879696 0.593100 0.413100 0.102 Uiso 1 1 calc R U . . .
C8 C 0.7968(2) 0.7674(3) 0.36534(14) 0.0594(6) Uani 1 1 d . . . . .
H8A H 0.769304 0.712840 0.323237 0.071 Uiso 1 1 calc R U . . .
H8B H 0.873600 0.828430 0.356109 0.071 Uiso 1 1 calc R U . . .
C9 C 0.6684(2) 0.8470(2) 0.38584(11) 0.0443(5) Uani 1 1 d . . . . .
H9 H 0.703070 0.932037 0.408729 0.053 Uiso 1 1 calc R U . . .
C10 C 0.5467(2) 0.8801(2) 0.32564(11) 0.0404(5) Uani 1 1 d . . . . .
C11 C 0.4278(2) 0.9543(2) 0.35993(11) 0.0438(5) Uani 1 1 d . . . . .
H11A H 0.458801 1.046612 0.371312 0.053 Uiso 1 1 calc R U . . .
H11B H 0.342042 0.959003 0.325774 0.053 Uiso 1 1 calc R U . . .
C12 C 0.3912(2) 0.8857(2) 0.42663(10) 0.0382(5) Uani 1 1 d . . . . .
C13 C 0.6075(2) 0.9715(2) 0.27299(13) 0.0502(6) Uani 1 1 d . . . . .
C14 C 0.5040(2) 0.7606(2) 0.27839(10) 0.0374(4) Uani 1 1 d . . . . .
C15 C 0.4362(2) 0.6315(2) 0.29598(10) 0.0386(5) Uani 1 1 d . . . . .
C16 C 0.5027(3) 0.5104(2) 0.28267(13) 0.0510(6) Uani 1 1 d . . . . .
H16 H 0.589876 0.511478 0.263946 0.061 Uiso 1 1 calc R U . . .
C17 C 0.4404(3) 0.3874(3) 0.29702(14) 0.0645(7) Uani 1 1 d . . . . .
H17 H 0.486145 0.306396 0.288231 0.077 Uiso 1 1 calc R U . . .
C18 C 0.3124(3) 0.3849(3) 0.32396(13) 0.0642(7) Uani 1 1 d . . . . .
H18 H 0.270711 0.302187 0.333385 0.077 Uiso 1 1 calc R U . . .
C19 C 0.2444(3) 0.5045(3) 0.33732(13) 0.0600(7) Uani 1 1 d . . . . .
H19 H 0.157106 0.502101 0.355895 0.072 Uiso 1 1 calc R U . . .
C20 C 0.3053(2) 0.6286(2) 0.32325(11) 0.0468(5) Uani 1 1 d . . . . .
H20 H 0.258778 0.709220 0.332018 0.056 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 C1 1.907(2) . ?
N1 C5 1.372(3) . ?
N1 C6 1.443(3) . ?
N1 C9 1.448(3) . ?
N2 C14 1.283(3) . ?
N2 O2 1.452(2) . ?
O1 C13 1.197(3) . ?
O2 C13 1.356(3) . ?
C1 C2 1.383(3) . ?
C1 C12 1.387(3) . ?
C2 C3 1.373(4) . ?
C2 H2 0.9300 . ?
C3 C4 1.374(3) . ?
C3 H3 0.9300 . ?
C4 C5 1.401(3) . ?
C4 H4 0.9300 . ?
C5 C12 1.408(3) . ?
C6 C7 1.499(4) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C7 C8 1.497(4) . ?
C7 H7A 0.9700 . ?
C7 H7B 0.9700 . ?
C8 C9 1.525(3) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C9 C10 1.547(3) . ?
C9 H9 0.9800 . ?
C10 C14 1.503(3) . ?
C10 C13 1.506(3) . ?
C10 C11 1.541(3) . ?
C11 C12 1.508(3) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C14 C15 1.477(3) . ?
C15 C16 1.383(3) . ?
C15 C20 1.389(3) . ?
C16 C17 1.385(4) . ?
C16 H16 0.9300 . ?
C17 C18 1.361(4) . ?
C17 H17 0.9300 . ?
C18 C19 1.376(4) . ?
C18 H18 0.9300 . ?
C19 C20 1.388(3) . ?
C19 H19 0.9300 . ?
C20 H20 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
C5 N1 C6 125.62(19) . . ?
C5 N1 C9 121.15(18) . . ?
C6 N1 C9 113.02(18) . . ?
C14 N2 O2 108.20(17) . . ?
C13 O2 N2 109.17(15) . . ?
C2 C1 C12 123.2(2) . . ?
C2 C1 Br1 117.87(17) . . ?
C12 C1 Br1 118.95(16) . . ?
C3 C2 C1 118.1(2) . . ?
C3 C2 H2 120.9 . . ?
C1 C2 H2 120.9 . . ?
C2 C3 C4 121.3(2) . . ?
C2 C3 H3 119.4 . . ?
C4 C3 H3 119.4 . . ?
C3 C4 C5 120.4(2) . . ?
C3 C4 H4 119.8 . . ?
C5 C4 H4 119.8 . . ?
N1 C5 C4 120.9(2) . . ?
N1 C5 C12 119.52(18) . . ?
C4 C5 C12 119.6(2) . . ?
N1 C6 C7 104.8(2) . . ?
N1 C6 H6A 110.8 . . ?
C7 C6 H6A 110.8 . . ?
N1 C6 H6B 110.8 . . ?
C7 C6 H6B 110.8 . . ?
H6A C6 H6B 108.9 . . ?
C8 C7 C6 106.7(2) . . ?
C8 C7 H7A 110.4 . . ?
C6 C7 H7A 110.4 . . ?
C8 C7 H7B 110.4 . . ?
C6 C7 H7B 110.4 . . ?
H7A C7 H7B 108.6 . . ?
C7 C8 C9 104.8(2) . . ?
C7 C8 H8A 110.8 . . ?
C9 C8 H8A 110.8 . . ?
C7 C8 H8B 110.8 . . ?
C9 C8 H8B 110.8 . . ?
H8A C8 H8B 108.9 . . ?
N1 C9 C8 103.62(19) . . ?
N1 C9 C10 109.62(16) . . ?
C8 C9 C10 117.05(18) . . ?
N1 C9 H9 108.7 . . ?
C8 C9 H9 108.7 . . ?
C10 C9 H9 108.7 . . ?
C14 C10 C13 99.67(17) . . ?
C14 C10 C11 117.92(17) . . ?
C13 C10 C11 110.37(17) . . ?
C14 C10 C9 113.15(17) . . ?
C13 C10 C9 108.01(17) . . ?
C11 C10 C9 107.20(17) . . ?
C12 C11 C10 113.03(17) . . ?
C12 C11 H11A 109.0 . . ?
C10 C11 H11A 109.0 . . ?
C12 C11 H11B 109.0 . . ?
C10 C11 H11B 109.0 . . ?
H11A C11 H11B 107.8 . . ?
C1 C12 C5 117.43(19) . . ?
C1 C12 C11 121.42(19) . . ?
C5 C12 C11 121.07(18) . . ?
O1 C13 O2 121.8(2) . . ?
O1 C13 C10 129.0(2) . . ?
O2 C13 C10 109.18(18) . . ?
N2 C14 C15 117.39(18) . . ?
N2 C14 C10 113.44(18) . . ?
C15 C14 C10 129.03(17) . . ?
C16 C15 C20 119.3(2) . . ?
C16 C15 C14 118.95(19) . . ?
C20 C15 C14 121.75(19) . . ?
C15 C16 C17 120.5(2) . . ?
C15 C16 H16 119.8 . . ?
C17 C16 H16 119.8 . . ?
C18 C17 C16 120.1(2) . . ?
C18 C17 H17 119.9 . . ?
C16 C17 H17 119.9 . . ?
C17 C18 C19 120.2(2) . . ?
C17 C18 H18 119.9 . . ?
C19 C18 H18 119.9 . . ?
C18 C19 C20 120.4(2) . . ?
C18 C19 H19 119.8 . . ?
C20 C19 H19 119.8 . . ?
C19 C20 C15 119.5(2) . . ?
C19 C20 H20 120.3 . . ?
C15 C20 H20 120.3 . . ?

_refine_diff_density_max         0.315
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.039



####################################################################### 
# 
# 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_0103
_database_code_depnum_ccdc_archive 'CCDC 2395319'
loop_
_audit_author_name
_audit_author_address
pmz-a
;Qingdao Agricultural University
China
;
_audit_update_record             
;
2024-11-01 deposited with the CCDC.	2025-01-02 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            'C22 H24 Br N3 O2'
_chemical_formula_weight         442.35

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'
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                   9.9945(5)
_cell_length_b                   10.0580(5)
_cell_length_c                   10.3299(5)
_cell_angle_alpha                90.047(2)
_cell_angle_beta                 98.948(2)
_cell_angle_gamma                102.789(2)
_cell_volume                     999.65(9)
_cell_formula_units_Z            2
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    3474
_cell_measurement_theta_min      2.078
_cell_measurement_theta_max      25.020

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            YELLOW
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.470
_exptl_crystal_F_000             456
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.401
_exptl_crystal_size_mid          0.333
_exptl_crystal_size_min          0.319
_exptl_absorpt_coefficient_mu    2.079
_shelx_estimated_absorpt_T_min   0.489
_shelx_estimated_absorpt_T_max   0.557
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.489
_exptl_absorpt_correction_T_max  0.557
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      273(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   MoK\a
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            15553
_diffrn_reflns_av_unetI/netI     0.0168
_diffrn_reflns_av_R_equivalents  0.0181
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.078
_diffrn_reflns_theta_max         25.020
_diffrn_reflns_theta_full        25.020
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measured_fraction_theta_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_point_group_measured_fraction_full 0.988
_reflns_number_total             3474
_reflns_number_gt                3118
_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    'SHELXL-2018/3 (Sheldrick, 2018)'
_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)+(0.0383P)²+0.3223P] 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         3474
_refine_ls_number_parameters     264
_refine_ls_number_restraints     36
_refine_ls_R_factor_all          0.0321
_refine_ls_R_factor_gt           0.0268
_refine_ls_wR_factor_ref         0.0704
_refine_ls_wR_factor_gt          0.0674
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_restrained_S_all      1.023
_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 0.76620(2) 0.84267(2) 0.46939(2) 0.05650(10) Uani 1 1 d . . . . .
N1 N 0.34867(17) 0.84791(17) 0.71795(16) 0.0472(4) Uani 1 1 d . . . . .
N2 N 0.27822(16) 0.52694(17) 0.34868(15) 0.0449(4) Uani 1 1 d . . . . .
H2A H 0.365277 0.528543 0.369757 0.054 Uiso 1 1 calc R U . . .
N3 N 0.23901(15) 0.47513(15) 0.68815(14) 0.0354(3) Uani 1 1 d . . . . .
H3A H 0.158593 0.479616 0.646826 0.042 Uiso 1 1 calc R U . . .
O1 O 0.09606(14) 0.59030(17) 0.40887(14) 0.0569(4) Uani 1 1 d . . . . .
O2 O 0.46910(13) 0.55611(15) 0.69213(14) 0.0517(4) Uani 1 1 d . . . . .
C1 C 0.68132(19) 0.90734(19) 0.60199(18) 0.0384(4) Uani 1 1 d . . . . .
C2 C 0.7638(2) 1.0105(2) 0.6874(2) 0.0470(5) Uani 1 1 d . . . . .
H2 H 0.856781 1.044827 0.680733 0.056 Uiso 1 1 calc R U . . .
C3 C 0.7034(2) 1.0601(2) 0.7823(2) 0.0497(5) Uani 1 1 d . . . . .
H3 H 0.756274 1.129611 0.840349 0.060 Uiso 1 1 calc R U . . .
C4 C 0.5661(2) 1.0090(2) 0.79287(19) 0.0470(5) Uani 1 1 d . . . . .
H4 H 0.527381 1.044039 0.857823 0.056 Uiso 1 1 calc R U . . .
C5 C 0.4843(2) 0.90437(18) 0.70635(17) 0.0386(4) Uani 1 1 d . . . . .
C6 C 0.2756(3) 0.9014(3) 0.8099(2) 0.0681(7) Uani 1 1 d . U . . .
H6A H 0.251475 0.986552 0.782677 0.082 Uiso 0.417(10) 1 d R U P A 1
H6B H 0.328442 0.913324 0.897837 0.082 Uiso 0.417(10) 1 d R U P A 1
H6C H 0.303484 1.000241 0.815932 0.082 Uiso 0.583(10) 1 d R U P A 2
H6D H 0.296706 0.866650 0.896454 0.082 Uiso 0.583(10) 1 d R U P A 2
C7 C 0.1482(7) 0.7804(10) 0.7982(7) 0.061(2) Uani 0.417(10) 1 d . U P A 1
H7A H 0.169883 0.706478 0.851874 0.073 Uiso 0.417(10) 1 calc R U P A 1
H7B H 0.070247 0.808503 0.826469 0.073 Uiso 0.417(10) 1 calc R U P A 1
C8 C 0.1157(2) 0.7375(2) 0.6616(2) 0.0511(5) Uani 1 1 d . U . . .
H8A H 0.047734 0.783153 0.614955 0.061 Uiso 0.417(10) 1 d R U P A 1
H8B H 0.078288 0.639803 0.652289 0.061 Uiso 0.417(10) 1 d R U P A 1
H8C H 0.037042 0.726098 0.591309 0.061 Uiso 0.583(10) 1 d R U P A 2
H8D H 0.109805 0.652957 0.707734 0.061 Uiso 0.583(10) 1 d R U P A 2
C9 C 0.25157(19) 0.77520(18) 0.60619(17) 0.0360(4) Uani 1 1 d . . . . .
H9 H 0.240272 0.841561 0.538244 0.043 Uiso 1 1 calc R U . . .
C10 C 0.31753(17) 0.66669(17) 0.54963(16) 0.0309(4) Uani 1 1 d . . . . .
C11 C 0.45496(18) 0.74465(18) 0.50869(17) 0.0353(4) Uani 1 1 d . . . . .
H11A H 0.509641 0.679287 0.493534 0.042 Uiso 1 1 calc R U . . .
H11B H 0.433359 0.787309 0.426221 0.042 Uiso 1 1 calc R U . . .
C12 C 0.54262(18) 0.85308(17) 0.60685(16) 0.0340(4) Uani 1 1 d . . . . .
C13 C 0.21979(18) 0.59144(18) 0.42798(16) 0.0337(4) Uani 1 1 d . . . . .
C14 C 0.2044(2) 0.4534(2) 0.2280(2) 0.0518(5) Uani 1 1 d . . . . .
H14A H 0.110476 0.410642 0.240381 0.062 Uiso 1 1 calc R U . . .
H14B H 0.250184 0.381749 0.209205 0.062 Uiso 1 1 calc R U . . .
C15 C 0.1981(3) 0.5438(3) 0.1131(2) 0.0765(8) Uani 1 1 d . . . . .
H15A H 0.151368 0.614102 0.130458 0.115 Uiso 1 1 calc R U . . .
H15B H 0.148206 0.490683 0.036373 0.115 Uiso 1 1 calc R U . . .
H15C H 0.290751 0.584705 0.098918 0.115 Uiso 1 1 calc R U . . .
C16 C 0.34942(17) 0.56077(17) 0.65051(16) 0.0320(4) Uani 1 1 d . . . . .
C17 C 0.24067(18) 0.37858(17) 0.78815(16) 0.0339(4) Uani 1 1 d . . . . .
C18 C 0.3581(2) 0.3733(2) 0.87772(19) 0.0475(5) Uani 1 1 d . . . . .
H18 H 0.442681 0.432254 0.871853 0.057 Uiso 1 1 calc R U . . .
C19 C 0.3484(2) 0.2799(2) 0.9756(2) 0.0550(5) Uani 1 1 d . . . . .
H19 H 0.427265 0.276480 1.035483 0.066 Uiso 1 1 calc R U . . .
C20 C 0.2246(3) 0.1919(2) 0.9860(2) 0.0542(5) Uani 1 1 d . . . . .
H20 H 0.218953 0.130321 1.053107 0.065 Uiso 1 1 calc R U . . .
C21 C 0.1098(2) 0.1961(2) 0.8967(2) 0.0545(5) Uani 1 1 d . . . . .
H21 H 0.025891 0.135837 0.902514 0.065 Uiso 1 1 calc R U . . .
C22 C 0.1165(2) 0.2884(2) 0.79790(19) 0.0440(4) Uani 1 1 d . . . . .
H22 H 0.037421 0.289929 0.737692 0.053 Uiso 1 1 calc R U . . .
C7' C 0.1168(5) 0.8563(6) 0.7538(6) 0.0588(15) Uani 0.583(10) 1 d . U P A 2
H7'1 H 0.061983 0.827019 0.822590 0.071 Uiso 0.583(10) 1 calc R U P A 2
H7'2 H 0.082899 0.928800 0.706839 0.071 Uiso 0.583(10) 1 calc R U 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
Br1 C1 1.9034(19) . ?
N1 C5 1.372(3) . ?
N1 C6 1.454(3) . ?
N1 C9 1.465(2) . ?
N2 C13 1.322(2) . ?
N2 C14 1.454(2) . ?
N2 H2A 0.8600 . ?
N3 C16 1.351(2) . ?
N3 C17 1.419(2) . ?
N3 H3A 0.8600 . ?
O1 C13 1.219(2) . ?
O2 C16 1.218(2) . ?
C1 C12 1.382(3) . ?
C1 C2 1.389(3) . ?
C2 C3 1.375(3) . ?
C2 H2 0.9300 . ?
C3 C4 1.376(3) . ?
C3 H3 0.9300 . ?
C4 C5 1.402(3) . ?
C4 H4 0.9300 . ?
C5 C12 1.408(3) . ?
C6 C7 1.544(7) . ?
C6 C7' 1.567(5) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C6 H6C 0.9700 . ?
C6 H6D 0.9700 . ?
C7 C8 1.441(6) . ?
C7 H7A 0.9700 . ?
C7 H7B 0.9700 . ?
C8 C7' 1.524(5) . ?
C8 C9 1.527(3) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C8 H8C 0.9700 . ?
C8 H8D 0.9700 . ?
C9 C10 1.551(2) . ?
C9 H9 0.9800 . ?
C10 C16 1.540(2) . ?
C10 C11 1.544(2) . ?
C10 C13 1.548(2) . ?
C11 C12 1.511(2) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C14 C15 1.498(4) . ?
C14 H14A 0.9700 . ?
C14 H14B 0.9700 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C17 C22 1.383(3) . ?
C17 C18 1.388(3) . ?
C18 C19 1.380(3) . ?
C18 H18 0.9300 . ?
C19 C20 1.372(3) . ?
C19 H19 0.9300 . ?
C20 C21 1.364(3) . ?
C20 H20 0.9300 . ?
C21 C22 1.380(3) . ?
C21 H21 0.9300 . ?
C22 H22 0.9300 . ?
C7' H7'1 0.9700 . ?
C7' H7'2 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
C5 N1 C6 122.82(16) . . ?
C5 N1 C9 120.66(15) . . ?
C6 N1 C9 111.23(16) . . ?
C13 N2 C14 124.06(16) . . ?
C13 N2 H2A 118.0 . . ?
C14 N2 H2A 118.0 . . ?
C16 N3 C17 127.36(14) . . ?
C16 N3 H3A 116.3 . . ?
C17 N3 H3A 116.3 . . ?
C12 C1 C2 123.64(19) . . ?
C12 C1 Br1 119.36(14) . . ?
C2 C1 Br1 116.98(15) . . ?
C3 C2 C1 117.71(19) . . ?
C3 C2 H2 121.1 . . ?
C1 C2 H2 121.1 . . ?
C2 C3 C4 121.27(18) . . ?
C2 C3 H3 119.4 . . ?
C4 C3 H3 119.4 . . ?
C3 C4 C5 120.38(19) . . ?
C3 C4 H4 119.8 . . ?
C5 C4 H4 119.8 . . ?
N1 C5 C4 121.56(18) . . ?
N1 C5 C12 118.78(16) . . ?
C4 C5 C12 119.65(18) . . ?
N1 C6 C7 97.4(3) . . ?
N1 C6 C7' 106.6(2) . . ?
N1 C6 H6A 112.5 . . ?
C7 C6 H6A 113.0 . . ?
N1 C6 H6B 111.8 . . ?
C7 C6 H6B 112.0 . . ?
H6A C6 H6B 109.7 . . ?
N1 C6 H6C 110.1 . . ?
C7' C6 H6C 109.6 . . ?
N1 C6 H6D 110.6 . . ?
C7' C6 H6D 111.4 . . ?
H6C C6 H6D 108.6 . . ?
C8 C7 C6 106.0(4) . . ?
C8 C7 H7A 110.5 . . ?
C6 C7 H7A 110.5 . . ?
C8 C7 H7B 110.5 . . ?
C6 C7 H7B 110.5 . . ?
H7A C7 H7B 108.7 . . ?
C7 C8 C9 106.6(3) . . ?
C7' C8 C9 105.9(2) . . ?
C7 C8 H8A 110.9 . . ?
C9 C8 H8A 110.2 . . ?
C7 C8 H8B 110.4 . . ?
C9 C8 H8B 110.2 . . ?
H8A C8 H8B 108.5 . . ?
C7' C8 H8C 110.2 . . ?
C9 C8 H8C 110.2 . . ?
C7' C8 H8D 111.3 . . ?
C9 C8 H8D 110.6 . . ?
H8C C8 H8D 108.6 . . ?
N1 C9 C8 102.27(15) . . ?
N1 C9 C10 108.86(14) . . ?
C8 C9 C10 122.47(16) . . ?
N1 C9 H9 107.5 . . ?
C8 C9 H9 107.5 . . ?
C10 C9 H9 107.5 . . ?
C16 C10 C11 108.95(14) . . ?
C16 C10 C13 108.89(13) . . ?
C11 C10 C13 109.54(14) . . ?
C16 C10 C9 112.63(14) . . ?
C11 C10 C9 106.55(14) . . ?
C13 C10 C9 110.22(14) . . ?
C12 C11 C10 115.02(14) . . ?
C12 C11 H11A 108.5 . . ?
C10 C11 H11A 108.5 . . ?
C12 C11 H11B 108.5 . . ?
C10 C11 H11B 108.5 . . ?
H11A C11 H11B 107.5 . . ?
C1 C12 C5 117.33(16) . . ?
C1 C12 C11 121.99(16) . . ?
C5 C12 C11 120.67(16) . . ?
O1 C13 N2 122.61(16) . . ?
O1 C13 C10 121.41(16) . . ?
N2 C13 C10 115.96(15) . . ?
N2 C14 C15 112.78(19) . . ?
N2 C14 H14A 109.0 . . ?
C15 C14 H14A 109.0 . . ?
N2 C14 H14B 109.0 . . ?
C15 C14 H14B 109.0 . . ?
H14A C14 H14B 107.8 . . ?
C14 C15 H15A 109.5 . . ?
C14 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C14 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
O2 C16 N3 122.93(16) . . ?
O2 C16 C10 120.44(16) . . ?
N3 C16 C10 116.63(14) . . ?
C22 C17 C18 119.05(17) . . ?
C22 C17 N3 117.33(15) . . ?
C18 C17 N3 123.59(17) . . ?
C19 C18 C17 119.59(19) . . ?
C19 C18 H18 120.2 . . ?
C17 C18 H18 120.2 . . ?
C20 C19 C18 121.1(2) . . ?
C20 C19 H19 119.4 . . ?
C18 C19 H19 119.4 . . ?
C21 C20 C19 119.1(2) . . ?
C21 C20 H20 120.4 . . ?
C19 C20 H20 120.4 . . ?
C20 C21 C22 120.9(2) . . ?
C20 C21 H21 119.5 . . ?
C22 C21 H21 119.5 . . ?
C21 C22 C17 120.17(19) . . ?
C21 C22 H22 119.9 . . ?
C17 C22 H22 119.9 . . ?
C8 C7' C6 100.9(3) . . ?
C8 C7' H7'1 111.6 . . ?
C6 C7' H7'1 111.6 . . ?
C8 C7' H7'2 111.6 . . ?
C6 C7' H7'2 111.6 . . ?
H7'1 C7' H7'2 109.4 . . ?

_refine_diff_density_max         0.245
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.035



