# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_mo_sp17_56_vesely
_database_code_depnum_ccdc_archive 'CCDC 1859005'
loop_
_audit_author_name
_audit_author_address
'Ivana Cisarova'
;Charles Univerzity
Czech Republic
;
_audit_update_record             
;
2018-07-29 deposited with the CCDC.	2019-03-04 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/1
_shelx_SHELXL_version_number     2018/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H19 Br N2 O3'
_chemical_formula_sum            'C22 H19 Br N2 O3'
_chemical_formula_weight         439.30
_chemical_compound_source        'synthesized by the authors'

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'
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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 21'
_space_group_name_Hall           'P 2yb'

_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+1/2, -z'

_cell_length_a                   9.6491(7)
_cell_length_b                   12.1125(9)
_cell_length_c                   9.7759(6)
_cell_angle_alpha                90
_cell_angle_beta                 117.882(2)
_cell_angle_gamma                90
_cell_volume                     1009.92(12)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    9960
_cell_measurement_theta_min      2.3880
_cell_measurement_theta_max      27.3255

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless-yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_F_000             448
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.358
_exptl_crystal_size_mid          0.275
_exptl_crystal_size_min          0.036
_exptl_absorpt_coefficient_mu    2.060
_shelx_estimated_absorpt_T_min   0.526
_shelx_estimated_absorpt_T_max   0.930
_exptl_absorpt_correction_type   'Numerical Mu From Formula'
_exptl_absorpt_correction_T_min  0.60
_exptl_absorpt_correction_T_max  0.93
_exptl_absorpt_process_details   
;
SADABS-2016/2 - Bruker AXS area detector scaling and absorption correction
;

_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'I\mS  micro-focus sealed tube'
_diffrn_radiation_monochromator  'Quazar Mo multilayer optic'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            23513
_diffrn_reflns_av_unetI/netI     0.0301
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.357
_diffrn_reflns_theta_max         27.556
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             4657
_reflns_number_gt                4266
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.907
_reflns_Friedel_fraction_max     0.996
_reflns_Friedel_fraction_full    1.000

_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 Instrument Service vV6.2.6'
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/1 (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)+(0.0293P)²+0.3375P] 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_abs_structure_details 
;
 Flack x determined using 1834 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.010(3)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         4657
_refine_ls_number_parameters     255
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0354
_refine_ls_R_factor_gt           0.0289
_refine_ls_wR_factor_ref         0.0650
_refine_ls_wR_factor_gt          0.0629
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_restrained_S_all      1.072
_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_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 0.70052(4) 0.87845(2) 0.04520(4) 0.04074(12) Uani 1 1 d . . . . .
O1 O 0.6578(3) 0.23194(18) 0.2886(3) 0.0239(5) Uani 1 1 d . . . . .
O2 O 0.3932(3) 0.5783(3) 0.4282(3) 0.0410(6) Uani 1 1 d . . . . .
O3 O 0.5522(3) 0.6117(2) 0.6785(3) 0.0410(7) Uani 1 1 d . . . . .
H3O H 0.462673 0.646774 0.665536 0.049 Uiso 1 1 d R U . . .
N1 N 0.8721(3) 0.3122(2) 0.2836(3) 0.0182(5) Uani 1 1 d . . . . .
N2 N 0.9818(3) 0.3969(2) 0.3632(3) 0.0235(6) Uani 1 1 d . . . . .
C1 C 0.9315(5) 0.1261(3) -0.0474(5) 0.0394(9) Uani 1 1 d . . . . .
H1 H 0.945483 0.084287 -0.122265 0.047 Uiso 1 1 calc R U . . .
C2 C 0.7894(4) 0.1275(3) -0.0478(4) 0.0292(7) Uani 1 1 d . . . . .
H2 H 0.704189 0.086755 -0.124129 0.035 Uiso 1 1 calc R U . . .
C3 C 0.7684(4) 0.1877(3) 0.0619(4) 0.0231(6) Uani 1 1 d . . . . .
H3 H 0.669909 0.187082 0.061759 0.028 Uiso 1 1 calc R U . . .
C4 C 0.8914(4) 0.2483(2) 0.1713(3) 0.0189(6) Uani 1 1 d . . . . .
C5 C 1.0360(4) 0.2485(3) 0.1730(4) 0.0310(7) Uani 1 1 d . . . . .
H5 H 1.120986 0.290304 0.247826 0.037 Uiso 1 1 calc R U . . .
C6 C 1.0539(5) 0.1861(4) 0.0629(5) 0.0428(10) Uani 1 1 d . . . . .
H6 H 1.152808 0.184915 0.063819 0.051 Uiso 1 1 calc R U . . .
C7 C 0.7632(3) 0.3009(2) 0.3332(3) 0.0173(6) Uani 1 1 d . . . . .
C8 C 0.7957(3) 0.3915(3) 0.4525(3) 0.0191(6) Uani 1 1 d . . . . .
C9 C 0.9400(4) 0.4423(2) 0.4565(4) 0.0229(6) Uani 1 1 d . . . . .
C10 C 1.0354(4) 0.5333(3) 0.5612(4) 0.0368(9) Uani 1 1 d . . . . .
H10A H 1.129316 0.545230 0.548753 0.055 Uiso 1 1 calc R U . . .
H10B H 1.066490 0.513138 0.668793 0.055 Uiso 1 1 calc R U . . .
H10C H 0.973006 0.601194 0.534851 0.055 Uiso 1 1 calc R U . . .
C11 C 0.8234(4) 0.3459(3) 0.6116(3) 0.0258(7) Uani 1 1 d . . . . .
H11A H 0.783087 0.269600 0.601336 0.031 Uiso 1 1 calc R U . . .
H11B H 0.936517 0.346243 0.686686 0.031 Uiso 1 1 calc R U . . .
C12 C 0.7343(4) 0.4231(3) 0.6624(4) 0.0253(7) Uani 1 1 d . . . . .
C13 C 0.7501(5) 0.4102(3) 0.8220(4) 0.0399(10) Uani 1 1 d . . . . .
H13A H 0.683795 0.464822 0.837450 0.060 Uiso 1 1 calc R U . . .
H13B H 0.859665 0.421548 0.899122 0.060 Uiso 1 1 calc R U . . .
H13C H 0.716995 0.335734 0.833344 0.060 Uiso 1 1 calc R U . . .
C14 C 0.6407(4) 0.4896(3) 0.5482(3) 0.0216(6) Uani 1 1 d . . . . .
C15 C 0.5152(4) 0.5627(3) 0.5439(4) 0.0263(7) Uani 1 1 d . . . . .
C16 C 0.6496(3) 0.4699(2) 0.3988(3) 0.0182(6) Uani 1 1 d . . . . .
H16 H 0.554403 0.427227 0.327103 0.022 Uiso 1 1 calc R U . . .
C17 C 0.6589(4) 0.5717(3) 0.3139(3) 0.0193(6) Uani 1 1 d . . . . .
C18 C 0.6408(3) 0.5609(3) 0.1650(3) 0.0198(6) Uani 1 1 d . . . . .
H18 H 0.620253 0.490090 0.117815 0.024 Uiso 1 1 calc R U . . .
C19 C 0.6519(4) 0.6515(3) 0.0834(4) 0.0225(6) Uani 1 1 d . . . . .
H19 H 0.639219 0.643074 -0.018425 0.027 Uiso 1 1 calc R U . . .
C20 C 0.6815(4) 0.7531(3) 0.1529(4) 0.0257(7) Uani 1 1 d . . . . .
C21 C 0.6994(4) 0.7678(3) 0.3003(4) 0.0301(7) Uani 1 1 d . . . . .
H21 H 0.718897 0.839039 0.346166 0.036 Uiso 1 1 calc R U . . .
C22 C 0.6881(4) 0.6760(3) 0.3804(4) 0.0267(7) Uani 1 1 d . . . . .
H22 H 0.700644 0.684979 0.482079 0.032 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 C20 1.905(3) . ?
O1 C7 1.228(4) . ?
O2 C15 1.207(4) . ?
O3 C15 1.331(4) . ?
O3 H3O 0.9166 . ?
N1 C7 1.354(4) . ?
N1 N2 1.417(3) . ?
N1 C4 1.426(4) . ?
N2 C9 1.281(4) . ?
C1 C2 1.370(5) . ?
C1 C6 1.377(6) . ?
C1 H1 0.9500 . ?
C2 C3 1.388(4) . ?
C2 H2 0.9500 . ?
C3 C4 1.380(4) . ?
C3 H3 0.9500 . ?
C4 C5 1.387(4) . ?
C5 C6 1.390(5) . ?
C5 H5 0.9500 . ?
C6 H6 0.9500 . ?
C7 C8 1.523(4) . ?
C8 C9 1.506(4) . ?
C8 C11 1.551(4) . ?
C8 C16 1.573(4) . ?
C9 C10 1.493(4) . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 C12 1.503(4) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C12 C14 1.329(4) . ?
C12 C13 1.503(4) . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 C15 1.484(4) . ?
C14 C16 1.522(4) . ?
C16 C17 1.512(4) . ?
C16 H16 1.0000 . ?
C17 C18 1.388(4) . ?
C17 C22 1.389(4) . ?
C18 C19 1.389(4) . ?
C18 H18 0.9500 . ?
C19 C20 1.370(5) . ?
C19 H19 0.9500 . ?
C20 C21 1.380(5) . ?
C21 C22 1.392(5) . ?
C21 H21 0.9500 . ?
C22 H22 0.9500 . ?

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
C15 O3 H3O 105.7 . . ?
C7 N1 N2 112.4(2) . . ?
C7 N1 C4 128.6(3) . . ?
N2 N1 C4 118.8(2) . . ?
C9 N2 N1 107.4(2) . . ?
C2 C1 C6 119.1(3) . . ?
C2 C1 H1 120.4 . . ?
C6 C1 H1 120.4 . . ?
C1 C2 C3 120.8(3) . . ?
C1 C2 H2 119.6 . . ?
C3 C2 H2 119.6 . . ?
C4 C3 C2 119.7(3) . . ?
C4 C3 H3 120.2 . . ?
C2 C3 H3 120.2 . . ?
C3 C4 C5 120.4(3) . . ?
C3 C4 N1 120.7(3) . . ?
C5 C4 N1 118.9(3) . . ?
C4 C5 C6 118.6(3) . . ?
C4 C5 H5 120.7 . . ?
C6 C5 H5 120.7 . . ?
C1 C6 C5 121.5(3) . . ?
C1 C6 H6 119.3 . . ?
C5 C6 H6 119.3 . . ?
O1 C7 N1 126.4(3) . . ?
O1 C7 C8 127.0(3) . . ?
N1 C7 C8 106.6(2) . . ?
C9 C8 C7 99.8(2) . . ?
C9 C8 C11 113.3(2) . . ?
C7 C8 C11 112.9(3) . . ?
C9 C8 C16 115.8(3) . . ?
C7 C8 C16 110.3(2) . . ?
C11 C8 C16 104.9(2) . . ?
N2 C9 C10 120.4(3) . . ?
N2 C9 C8 113.7(3) . . ?
C10 C9 C8 125.8(3) . . ?
C9 C10 H10A 109.5 . . ?
C9 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C9 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C12 C11 C8 104.7(2) . . ?
C12 C11 H11A 110.8 . . ?
C8 C11 H11A 110.8 . . ?
C12 C11 H11B 110.8 . . ?
C8 C11 H11B 110.8 . . ?
H11A C11 H11B 108.9 . . ?
C14 C12 C13 129.3(3) . . ?
C14 C12 C11 111.6(3) . . ?
C13 C12 C11 118.8(3) . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C12 C14 C15 127.6(3) . . ?
C12 C14 C16 112.9(3) . . ?
C15 C14 C16 118.5(3) . . ?
O2 C15 O3 123.3(3) . . ?
O2 C15 C14 123.1(3) . . ?
O3 C15 C14 113.6(3) . . ?
C17 C16 C14 116.4(2) . . ?
C17 C16 C8 113.7(2) . . ?
C14 C16 C8 102.6(2) . . ?
C17 C16 H16 107.9 . . ?
C14 C16 H16 107.9 . . ?
C8 C16 H16 107.9 . . ?
C18 C17 C22 118.3(3) . . ?
C18 C17 C16 119.2(3) . . ?
C22 C17 C16 122.4(3) . . ?
C17 C18 C19 121.5(3) . . ?
C17 C18 H18 119.3 . . ?
C19 C18 H18 119.3 . . ?
C20 C19 C18 118.6(3) . . ?
C20 C19 H19 120.7 . . ?
C18 C19 H19 120.7 . . ?
C19 C20 C21 121.9(3) . . ?
C19 C20 Br1 119.6(3) . . ?
C21 C20 Br1 118.5(3) . . ?
C20 C21 C22 118.7(3) . . ?
C20 C21 H21 120.7 . . ?
C22 C21 H21 120.7 . . ?
C17 C22 C21 121.0(3) . . ?
C17 C22 H22 119.5 . . ?
C21 C22 H22 119.5 . . ?

_refine_diff_density_max         0.506
_refine_diff_density_min         -0.521
_refine_diff_density_rms         0.052

####################################################################### 
# 
# 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_mo_sp17_57_vesely
_database_code_depnum_ccdc_archive 'CCDC 1859006'
loop_
_audit_author_name
_audit_author_address
'Ivana Cisarova'
;Charles Univerzity
Czech Republic
;
_audit_update_record             
;
2018-07-29 deposited with the CCDC.	2019-03-04 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/1
_shelx_SHELXL_version_number     2018/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H19 Br N2 O3'
_chemical_formula_sum            'C22 H19 Br N2 O3'
_chemical_formula_weight         439.30
_chemical_compound_source        'synthesized by the authors'

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'
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'

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

_cell_length_a                   10.3176(3)
_cell_length_b                   10.5583(3)
_cell_length_c                   18.2395(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1986.94(10)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    9861
_cell_measurement_theta_min      2.2288
_cell_measurement_theta_max      27.4783

_exptl_crystal_description       plate
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.469
_exptl_crystal_F_000             896
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.280
_exptl_crystal_size_mid          0.265
_exptl_crystal_size_min          0.184
_exptl_absorpt_coefficient_mu    2.094
_shelx_estimated_absorpt_T_min   0.592
_shelx_estimated_absorpt_T_max   0.699
_exptl_absorpt_correction_type   'Numerical Mu From Formula'
_exptl_absorpt_correction_T_min  0.42
_exptl_absorpt_correction_T_max  0.70
_exptl_absorpt_process_details   
;
SADABS-2016/2 - Bruker AXS area detector scaling and absorption correction
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'I\mS  micro-focus sealed tube'
_diffrn_radiation_monochromator  'Quazar Mo multilayer optic'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Kappa Duo PHOTON 100 CMOS'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            21982
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.229
_diffrn_reflns_theta_max         27.494
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             4570
_reflns_number_gt                4322
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.758
_reflns_Friedel_fraction_max     0.998
_reflns_Friedel_fraction_full    0.998

_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 Instrument Service vV6.2.6'
_computing_cell_refinement       'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_data_reduction        'SAINT V8.38A (Bruker AXS Inc., 2017)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/1 (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)+(0.0314P)²+0.3255P] 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_abs_structure_details 
;
 Flack x determined using 1777 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(2)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         4570
_refine_ls_number_parameters     255
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0254
_refine_ls_R_factor_gt           0.0225
_refine_ls_wR_factor_ref         0.0561
_refine_ls_wR_factor_gt          0.0549
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_restrained_S_all      1.054
_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 -0.06731(2) 0.56590(3) 0.13786(2) 0.03431(8) Uani 1 1 d . . . . .
O1 O 0.23546(14) 0.40979(14) 0.36214(8) 0.0215(3) Uani 1 1 d . . . . .
O2 O 0.48640(18) 0.86268(17) 0.25703(10) 0.0320(4) Uani 1 1 d . . . . .
O3 O 0.67619(17) 0.76129(18) 0.24706(10) 0.0310(4) Uani 1 1 d . . . . .
H3O H 0.694199 0.821254 0.214744 0.037 Uiso 1 1 d R U . . .
N1 N 0.18316(18) 0.51192(18) 0.47006(10) 0.0200(4) Uani 1 1 d . . . . .
N2 N 0.2424(2) 0.59984(19) 0.51841(10) 0.0253(4) Uani 1 1 d . . . . .
C1 C -0.1600(3) 0.3350(3) 0.53891(17) 0.0383(7) Uani 1 1 d . . . . .
H1 H -0.236839 0.293946 0.555047 0.046 Uiso 1 1 calc R U . . .
C2 C -0.0912(3) 0.4112(3) 0.58629(15) 0.0401(7) Uani 1 1 d . . . . .
H2 H -0.121724 0.423495 0.634901 0.048 Uiso 1 1 calc R U . . .
C3 C 0.0222(3) 0.4700(3) 0.56383(13) 0.0310(6) Uani 1 1 d . . . . .
H3 H 0.069289 0.522444 0.596754 0.037 Uiso 1 1 calc R U . . .
C4 C 0.0664(2) 0.4515(2) 0.49242(11) 0.0214(4) Uani 1 1 d . . . . .
C5 C -0.0037(2) 0.3774(3) 0.44399(14) 0.0309(6) Uani 1 1 d . . . . .
H5 H 0.025184 0.366833 0.394911 0.037 Uiso 1 1 calc R U . . .
C6 C -0.1168(3) 0.3185(3) 0.46768(19) 0.0395(7) Uani 1 1 d . . . . .
H6 H -0.164686 0.266754 0.434803 0.047 Uiso 1 1 calc R U . . .
C7 C 0.2579(2) 0.4889(2) 0.40955(11) 0.0177(4) Uani 1 1 d . . . . .
C8 C 0.3736(2) 0.5773(2) 0.41511(11) 0.0194(4) Uani 1 1 d . . . . .
C9 C 0.3491(2) 0.6349(2) 0.48892(12) 0.0238(5) Uani 1 1 d . . . . .
C10 C 0.4359(3) 0.7279(3) 0.52569(13) 0.0395(6) Uani 1 1 d . . . . .
H10A H 0.525539 0.697397 0.523579 0.059 Uiso 1 1 calc R U . . .
H10B H 0.409605 0.737627 0.577013 0.059 Uiso 1 1 calc R U . . .
H10C H 0.429676 0.809808 0.500701 0.059 Uiso 1 1 calc R U . . .
C11 C 0.5032(2) 0.5048(2) 0.40694(13) 0.0249(5) Uani 1 1 d . . . . .
H11A H 0.547616 0.497869 0.454892 0.030 Uiso 1 1 calc R U . . .
H11B H 0.487913 0.418566 0.387543 0.030 Uiso 1 1 calc R U . . .
C12 C 0.5832(2) 0.5809(2) 0.35425(12) 0.0230(4) Uani 1 1 d . . . . .
C13 C 0.7189(2) 0.5375(3) 0.33947(15) 0.0358(6) Uani 1 1 d . . . . .
H13A H 0.716843 0.454342 0.315622 0.054 Uiso 1 1 calc R U . . .
H13B H 0.766465 0.531170 0.385853 0.054 Uiso 1 1 calc R U . . .
H13C H 0.762330 0.598532 0.307289 0.054 Uiso 1 1 calc R U . . .
C14 C 0.5158(2) 0.6769(2) 0.32640(11) 0.0191(4) Uani 1 1 d . . . . .
C15 C 0.5564(2) 0.7757(2) 0.27398(11) 0.0219(4) Uani 1 1 d . . . . .
C16 C 0.3768(2) 0.6846(2) 0.35378(11) 0.0182(4) Uani 1 1 d . . . . .
H16 H 0.363591 0.768687 0.377844 0.022 Uiso 1 1 calc R U . . .
C17 C 0.2739(2) 0.6670(2) 0.29564(11) 0.0181(4) Uani 1 1 d . . . . .
C18 C 0.2942(2) 0.5889(2) 0.23541(11) 0.0206(5) Uani 1 1 d . . . . .
H18 H 0.377851 0.554333 0.226870 0.025 Uiso 1 1 calc R U . . .
C19 C 0.1936(2) 0.5608(3) 0.18761(12) 0.0248(5) Uani 1 1 d . . . . .
H19 H 0.208024 0.507147 0.146585 0.030 Uiso 1 1 calc R U . . .
C20 C 0.0729(2) 0.6113(2) 0.20024(12) 0.0234(4) Uani 1 1 d . . . . .
C21 C 0.0505(2) 0.6945(2) 0.25759(14) 0.0284(5) Uani 1 1 d . . . . .
H21 H -0.032222 0.732157 0.264384 0.034 Uiso 1 1 calc R U . . .
C22 C 0.1527(2) 0.7214(2) 0.30498(13) 0.0244(5) Uani 1 1 d . . . . .
H22 H 0.139003 0.778302 0.344589 0.029 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 C20 1.902(2) . ?
O1 C7 1.225(3) . ?
O2 C15 1.209(3) . ?
O3 C15 1.338(3) . ?
O3 H3O 0.8848 . ?
N1 C7 1.368(3) . ?
N1 N2 1.419(3) . ?
N1 C4 1.423(3) . ?
N2 C9 1.281(3) . ?
C1 C2 1.378(4) . ?
C1 C6 1.384(4) . ?
C1 H1 0.9500 . ?
C2 C3 1.387(4) . ?
C2 H2 0.9500 . ?
C3 C4 1.394(3) . ?
C3 H3 0.9500 . ?
C4 C5 1.384(3) . ?
C5 C6 1.391(3) . ?
C5 H5 0.9500 . ?
C6 H6 0.9500 . ?
C7 C8 1.519(3) . ?
C8 C9 1.498(3) . ?
C8 C11 1.548(3) . ?
C8 C16 1.592(3) . ?
C9 C10 1.488(3) . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 C12 1.500(3) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C12 C14 1.329(3) . ?
C12 C13 1.499(3) . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 C15 1.476(3) . ?
C14 C16 1.521(3) . ?
C16 C17 1.512(3) . ?
C16 H16 1.0000 . ?
C17 C22 1.387(3) . ?
C17 C18 1.390(3) . ?
C18 C19 1.387(3) . ?
C18 H18 0.9500 . ?
C19 C20 1.374(3) . ?
C19 H19 0.9500 . ?
C20 C21 1.385(3) . ?
C21 C22 1.392(3) . ?
C21 H21 0.9500 . ?
C22 H22 0.9500 . ?

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
C15 O3 H3O 110.9 . . ?
C7 N1 N2 112.01(18) . . ?
C7 N1 C4 128.97(19) . . ?
N2 N1 C4 118.67(17) . . ?
C9 N2 N1 107.35(18) . . ?
C2 C1 C6 119.7(2) . . ?
C2 C1 H1 120.1 . . ?
C6 C1 H1 120.1 . . ?
C1 C2 C3 120.8(2) . . ?
C1 C2 H2 119.6 . . ?
C3 C2 H2 119.6 . . ?
C2 C3 C4 119.3(3) . . ?
C2 C3 H3 120.4 . . ?
C4 C3 H3 120.4 . . ?
C5 C4 C3 120.3(2) . . ?
C5 C4 N1 120.87(19) . . ?
C3 C4 N1 118.8(2) . . ?
C4 C5 C6 119.5(2) . . ?
C4 C5 H5 120.2 . . ?
C6 C5 H5 120.2 . . ?
C1 C6 C5 120.4(3) . . ?
C1 C6 H6 119.8 . . ?
C5 C6 H6 119.8 . . ?
O1 C7 N1 125.7(2) . . ?
O1 C7 C8 127.97(19) . . ?
N1 C7 C8 106.28(18) . . ?
C9 C8 C7 100.17(17) . . ?
C9 C8 C11 115.63(18) . . ?
C7 C8 C11 111.64(19) . . ?
C9 C8 C16 110.26(19) . . ?
C7 C8 C16 114.00(17) . . ?
C11 C8 C16 105.42(16) . . ?
N2 C9 C10 121.2(2) . . ?
N2 C9 C8 113.9(2) . . ?
C10 C9 C8 124.8(2) . . ?
C9 C10 H10A 109.5 . . ?
C9 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C9 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C12 C11 C8 105.78(19) . . ?
C12 C11 H11A 110.6 . . ?
C8 C11 H11A 110.6 . . ?
C12 C11 H11B 110.6 . . ?
C8 C11 H11B 110.6 . . ?
H11A C11 H11B 108.7 . . ?
C14 C12 C13 130.8(2) . . ?
C14 C12 C11 111.44(19) . . ?
C13 C12 C11 117.7(2) . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C12 C14 C15 129.6(2) . . ?
C12 C14 C16 114.09(19) . . ?
C15 C14 C16 116.3(2) . . ?
O2 C15 O3 123.0(2) . . ?
O2 C15 C14 122.2(2) . . ?
O3 C15 C14 114.8(2) . . ?
C17 C16 C14 115.18(17) . . ?
C17 C16 C8 113.00(17) . . ?
C14 C16 C8 102.27(17) . . ?
C17 C16 H16 108.7 . . ?
C14 C16 H16 108.7 . . ?
C8 C16 H16 108.7 . . ?
C22 C17 C18 118.6(2) . . ?
C22 C17 C16 119.8(2) . . ?
C18 C17 C16 121.41(19) . . ?
C19 C18 C17 120.7(2) . . ?
C19 C18 H18 119.6 . . ?
C17 C18 H18 119.6 . . ?
C20 C19 C18 119.3(2) . . ?
C20 C19 H19 120.4 . . ?
C18 C19 H19 120.4 . . ?
C19 C20 C21 121.6(2) . . ?
C19 C20 Br1 119.41(17) . . ?
C21 C20 Br1 118.98(19) . . ?
C20 C21 C22 118.2(2) . . ?
C20 C21 H21 120.9 . . ?
C22 C21 H21 120.9 . . ?
C17 C22 C21 121.5(2) . . ?
C17 C22 H22 119.3 . . ?
C21 C22 H22 119.3 . . ?

_refine_diff_density_max         0.216
_refine_diff_density_min         -0.430
_refine_diff_density_rms         0.063

