# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1869248'
_audit_update_record             
;
2018-09-23 deposited with the CCDC.
2018-10-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C25 H23 Br N2'
_chemical_formula_sum            'C25 H23 Br N2'
_chemical_formula_weight         431.35

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'
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           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

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

_cell_length_a                   13.2298(3)
_cell_length_b                   10.1625(3)
_cell_length_c                   15.5329(5)
_cell_angle_alpha                90
_cell_angle_beta                 98.015(2)
_cell_angle_gamma                90
_cell_volume                     2067.96(10)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    5477
_cell_measurement_theta_min      3.6800
_cell_measurement_theta_max      27.2930

_exptl_crystal_description       BLOCK
_exptl_crystal_colour            RED
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.386
_exptl_crystal_F_000             888
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.240
_exptl_crystal_size_mid          0.220
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    2.000
_shelx_estimated_absorpt_T_min   0.645
_shelx_estimated_absorpt_T_max   0.690
_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      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'xcalibur sapphire3'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            24676
_diffrn_reflns_av_unetI/netI     0.0285
_diffrn_reflns_av_R_equivalents  0.0435
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         3.322
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3631
_reflns_number_gt                3031
_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       'CrysAlisPro, Oxford Diffraction Ltd.,'
_computing_cell_refinement       'CrysAlisPro, Oxford Diffraction Ltd.,'
_computing_data_reduction        'CrysAlisPro, Oxford Diffraction Ltd.,'
_computing_structure_solution    'SHELXL-2016/6 (Sheldrick, 2016)'
_computing_structure_refinement  'SHELXL-2016/6 (Sheldrick, 2016)'
_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)+(0.0667P)²+2.2654P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3631
_refine_ls_number_parameters     293
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0421
_refine_ls_wR_factor_ref         0.1131
_refine_ls_wR_factor_gt          0.1059
_refine_ls_goodness_of_fit_ref   0.918
_refine_ls_restrained_S_all      0.918
_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
Br Br 0.27077(3) 0.51567(4) -0.03531(2) 0.05438(16) Uani 1 1 d . . . . .
N1 N 0.86540(17) 0.1873(2) 0.28849(15) 0.0305(5) Uani 1 1 d . . . . .
C9 C 0.7858(2) 0.2736(3) 0.30117(18) 0.0277(6) Uani 1 1 d . . . . .
C10 C 0.7920(2) 0.3408(3) 0.38080(18) 0.0293(6) Uani 1 1 d . . . . .
N2 N 0.9540(2) 0.3045(3) 0.4915(2) 0.0568(8) Uani 1 1 d . . . . .
C8 C 0.7028(2) 0.2994(3) 0.23806(18) 0.0305(6) Uani 1 1 d . . . . .
H8 H 0.698225 0.256830 0.184667 0.037 Uiso 1 1 calc R U . . .
C13 C 0.7211(2) 0.5030(3) 0.48107(19) 0.0306(6) Uani 1 1 d . . . . .
C7 C 0.6265(2) 0.3871(3) 0.25270(18) 0.0301(6) Uani 1 1 d . . . . .
C6 C 0.5386(2) 0.4165(3) 0.18455(19) 0.0314(6) Uani 1 1 d . . . . .
C3 C 0.3787(2) 0.4736(3) 0.0543(2) 0.0375(7) Uani 1 1 d . . . . .
C12 C 0.6339(2) 0.4492(3) 0.33332(19) 0.0317(6) Uani 1 1 d . . . . .
H12 H 0.582091 0.506070 0.344122 0.038 Uiso 1 1 calc R U . . .
C11 C 0.7156(2) 0.4292(3) 0.39782(18) 0.0304(6) Uani 1 1 d . . . . .
C17 C 0.8024(2) 0.6612(3) 0.5832(2) 0.0384(7) Uani 1 1 d . . . . .
H17 H 0.856865 0.717696 0.600142 0.046 Uiso 1 1 calc R U . . .
C20 C 0.8818(2) 0.3218(3) 0.44380(19) 0.0360(7) Uani 1 1 d . . . . .
C18 C 0.8012(2) 0.5883(3) 0.5086(2) 0.0368(7) Uani 1 1 d . . . . .
H18 H 0.854832 0.596055 0.475998 0.044 Uiso 1 1 calc R U . . .
C2 C 0.4194(2) 0.3491(3) 0.0598(2) 0.0417(8) Uani 1 1 d . . . . .
H2 H 0.393460 0.284261 0.020542 0.050 Uiso 1 1 calc R U . . .
C16 C 0.7242(2) 0.6523(3) 0.63360(19) 0.0375(7) Uani 1 1 d . . . . .
C14 C 0.6431(2) 0.4928(3) 0.5319(2) 0.0386(7) Uani 1 1 d . . . . .
H14 H 0.588727 0.436075 0.515243 0.046 Uiso 1 1 calc R U . . .
C1 C 0.4994(2) 0.3213(3) 0.1243(2) 0.0385(7) Uani 1 1 d . . . . .
H1 H 0.527738 0.237417 0.127552 0.046 Uiso 1 1 calc R U . . .
C4 C 0.4146(2) 0.5701(3) 0.1129(2) 0.0416(8) Uani 1 1 d . . . . .
H4 H 0.386129 0.653902 0.108888 0.050 Uiso 1 1 calc R U . . .
C25 C 0.8826(2) 0.1591(3) 0.1993(2) 0.0361(7) Uani 1 1 d . . . . .
C15 C 0.6456(2) 0.5662(3) 0.6069(2) 0.0428(8) Uani 1 1 d . . . . .
H15 H 0.592873 0.557200 0.640360 0.051 Uiso 1 1 calc R U . . .
C21 C 0.8769(3) 0.0689(3) 0.3428(2) 0.0397(7) Uani 1 1 d . . . . .
C5 C 0.4941(2) 0.5399(3) 0.1779(2) 0.0399(7) Uani 1 1 d . . . . .
H5 H 0.518032 0.604423 0.218096 0.048 Uiso 1 1 calc R U . . .
C24 C 0.9902(3) 0.1080(4) 0.2009(3) 0.0483(9) Uani 1 1 d . . . . .
C19 C 0.7256(3) 0.7339(4) 0.7154(2) 0.0561(10) Uani 1 1 d . . . . .
H19A H 0.785775 0.787713 0.723432 0.084 Uiso 1 1 calc R U . . .
H19B H 0.666119 0.789074 0.710109 0.084 Uiso 1 1 calc R U . . .
H19C H 0.725680 0.676565 0.764556 0.084 Uiso 1 1 calc R U . . .
C22 C 0.9848(3) 0.0165(4) 0.3491(3) 0.0517(9) Uani 1 1 d . . . . .
C23 C 1.0121(4) -0.0096(4) 0.2594(3) 0.0554(10) Uani 1 1 d . . . . .
H21 H 0.872(2) 0.236(3) 0.1678(19) 0.033(8) Uiso 1 1 d . . . . .
H20 H 0.837(2) 0.094(3) 0.171(2) 0.037(8) Uiso 1 1 d . . . . .
H23 H 0.862(2) 0.090(3) 0.397(2) 0.046(10) Uiso 1 1 d . . . . .
H22 H 0.827(3) 0.002(3) 0.315(2) 0.050(10) Uiso 1 1 d . . . . .
H29 H 1.034(3) 0.183(4) 0.221(2) 0.052(10) Uiso 1 1 d . . . . .
H28 H 0.999(3) 0.088(4) 0.143(3) 0.058(11) Uiso 1 1 d . . . . .
H25 H 1.034(3) 0.085(4) 0.382(2) 0.058(11) Uiso 1 1 d . . . . .
H24 H 0.990(3) -0.065(4) 0.384(3) 0.065(11) Uiso 1 1 d . . . . .
H27 H 1.084(4) -0.033(4) 0.265(3) 0.075(13) Uiso 1 1 d . . . . .
H26 H 0.971(3) -0.082(5) 0.235(3) 0.073(13) Uiso 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
Br C3 1.899(3) . ?
N1 C9 1.405(3) . ?
N1 C25 1.464(4) . ?
N1 C21 1.465(4) . ?
C9 C8 1.391(4) . ?
C9 C10 1.405(4) . ?
C10 C11 1.405(4) . ?
C10 C20 1.442(4) . ?
N2 C20 1.138(4) . ?
C8 C7 1.388(4) . ?
C8 H8 0.9300 . ?
C13 C18 1.390(4) . ?
C13 C14 1.388(4) . ?
C13 C11 1.488(4) . ?
C7 C12 1.393(4) . ?
C7 C6 1.489(4) . ?
C6 C5 1.384(4) . ?
C6 C1 1.395(4) . ?
C3 C2 1.373(4) . ?
C3 C4 1.376(5) . ?
C12 C11 1.383(4) . ?
C12 H12 0.9300 . ?
C17 C18 1.374(4) . ?
C17 C16 1.386(4) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
C2 C1 1.381(4) . ?
C2 H2 0.9300 . ?
C16 C15 1.378(4) . ?
C16 C19 1.515(4) . ?
C14 C15 1.380(5) . ?
C14 H14 0.9300 . ?
C1 H1 0.9300 . ?
C4 C5 1.387(4) . ?
C4 H4 0.9300 . ?
C25 C24 1.512(4) . ?
C25 H21 0.92(3) . ?
C25 H20 0.97(3) . ?
C15 H15 0.9300 . ?
C21 C22 1.514(5) . ?
C21 H23 0.92(3) . ?
C21 H22 1.01(4) . ?
C5 H5 0.9300 . ?
C24 C23 1.504(5) . ?
C24 H29 0.98(4) . ?
C24 H28 0.95(4) . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C22 C23 1.511(6) . ?
C22 H25 1.03(4) . ?
C22 H24 0.99(4) . ?
C23 H27 0.97(5) . ?
C23 H26 0.96(4) . ?

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
C9 N1 C25 118.3(2) . . ?
C9 N1 C21 116.8(2) . . ?
C25 N1 C21 111.5(2) . . ?
C8 C9 C10 118.2(2) . . ?
C8 C9 N1 123.5(2) . . ?
C10 C9 N1 118.2(2) . . ?
C11 C10 C9 121.4(2) . . ?
C11 C10 C20 120.2(3) . . ?
C9 C10 C20 118.3(2) . . ?
C7 C8 C9 121.7(3) . . ?
C7 C8 H8 119.1 . . ?
C9 C8 H8 119.1 . . ?
C18 C13 C14 117.9(3) . . ?
C18 C13 C11 121.6(3) . . ?
C14 C13 C11 120.5(3) . . ?
C8 C7 C12 118.4(3) . . ?
C8 C7 C6 121.7(3) . . ?
C12 C7 C6 119.9(2) . . ?
C5 C6 C1 117.6(3) . . ?
C5 C6 C7 121.2(3) . . ?
C1 C6 C7 121.2(3) . . ?
C2 C3 C4 121.3(3) . . ?
C2 C3 Br 120.1(2) . . ?
C4 C3 Br 118.6(2) . . ?
C11 C12 C7 122.3(3) . . ?
C11 C12 H12 118.8 . . ?
C7 C12 H12 118.8 . . ?
C12 C11 C10 117.9(3) . . ?
C12 C11 C13 119.6(3) . . ?
C10 C11 C13 122.5(2) . . ?
C18 C17 C16 121.3(3) . . ?
C18 C17 H17 119.3 . . ?
C16 C17 H17 119.3 . . ?
N2 C20 C10 177.7(3) . . ?
C17 C18 C13 120.9(3) . . ?
C17 C18 H18 119.5 . . ?
C13 C18 H18 119.5 . . ?
C3 C2 C1 119.2(3) . . ?
C3 C2 H2 120.4 . . ?
C1 C2 H2 120.4 . . ?
C15 C16 C17 117.6(3) . . ?
C15 C16 C19 121.4(3) . . ?
C17 C16 C19 121.1(3) . . ?
C15 C14 C13 120.5(3) . . ?
C15 C14 H14 119.7 . . ?
C13 C14 H14 119.7 . . ?
C2 C1 C6 121.4(3) . . ?
C2 C1 H1 119.3 . . ?
C6 C1 H1 119.3 . . ?
C3 C4 C5 118.7(3) . . ?
C3 C4 H4 120.6 . . ?
C5 C4 H4 120.6 . . ?
N1 C25 C24 108.8(3) . . ?
N1 C25 H21 107.6(18) . . ?
C24 C25 H21 111.8(18) . . ?
N1 C25 H20 113.4(19) . . ?
C24 C25 H20 107.6(18) . . ?
H21 C25 H20 108(3) . . ?
C16 C15 C14 121.7(3) . . ?
C16 C15 H15 119.2 . . ?
C14 C15 H15 119.2 . . ?
N1 C21 C22 110.4(3) . . ?
N1 C21 H23 108(2) . . ?
C22 C21 H23 110(2) . . ?
N1 C21 H22 107(2) . . ?
C22 C21 H22 110(2) . . ?
H23 C21 H22 110(3) . . ?
C6 C5 C4 121.8(3) . . ?
C6 C5 H5 119.1 . . ?
C4 C5 H5 119.1 . . ?
C25 C24 C23 112.7(3) . . ?
C25 C24 H29 105(2) . . ?
C23 C24 H29 112(2) . . ?
C25 C24 H28 107(2) . . ?
C23 C24 H28 111(2) . . ?
H29 C24 H28 109(3) . . ?
C16 C19 H19A 109.5 . . ?
C16 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C16 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C23 C22 C21 110.3(3) . . ?
C23 C22 H25 111(2) . . ?
C21 C22 H25 108(2) . . ?
C23 C22 H24 111(2) . . ?
C21 C22 H24 109(2) . . ?
H25 C22 H24 108(3) . . ?
C22 C23 C24 111.5(3) . . ?
C22 C23 H27 108(3) . . ?
C24 C23 H27 111(3) . . ?
C22 C23 H26 107(3) . . ?
C24 C23 H26 109(3) . . ?
H27 C23 H26 110(4) . . ?

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
C25 N1 C9 C8 22.1(4) . . . . ?
C21 N1 C9 C8 -115.4(3) . . . . ?
C25 N1 C9 C10 -155.6(3) . . . . ?
C21 N1 C9 C10 66.8(3) . . . . ?
C8 C9 C10 C11 1.7(4) . . . . ?
N1 C9 C10 C11 179.6(2) . . . . ?
C8 C9 C10 C20 -175.4(3) . . . . ?
N1 C9 C10 C20 2.5(4) . . . . ?
C10 C9 C8 C7 -1.1(4) . . . . ?
N1 C9 C8 C7 -178.9(3) . . . . ?
C9 C8 C7 C12 -0.6(4) . . . . ?
C9 C8 C7 C6 178.9(3) . . . . ?
C8 C7 C6 C5 -146.8(3) . . . . ?
C12 C7 C6 C5 32.6(4) . . . . ?
C8 C7 C6 C1 32.1(4) . . . . ?
C12 C7 C6 C1 -148.5(3) . . . . ?
C8 C7 C12 C11 1.8(4) . . . . ?
C6 C7 C12 C11 -177.6(3) . . . . ?
C7 C12 C11 C10 -1.3(4) . . . . ?
C7 C12 C11 C13 177.4(3) . . . . ?
C9 C10 C11 C12 -0.5(4) . . . . ?
C20 C10 C11 C12 176.5(3) . . . . ?
C9 C10 C11 C13 -179.1(3) . . . . ?
C20 C10 C11 C13 -2.1(4) . . . . ?
C18 C13 C11 C12 -118.9(3) . . . . ?
C14 C13 C11 C12 58.2(4) . . . . ?
C18 C13 C11 C10 59.7(4) . . . . ?
C14 C13 C11 C10 -123.2(3) . . . . ?
C16 C17 C18 C13 0.1(5) . . . . ?
C14 C13 C18 C17 -0.8(5) . . . . ?
C11 C13 C18 C17 176.4(3) . . . . ?
C4 C3 C2 C1 -1.4(5) . . . . ?
Br C3 C2 C1 178.5(2) . . . . ?
C18 C17 C16 C15 0.9(5) . . . . ?
C18 C17 C16 C19 -179.5(3) . . . . ?
C18 C13 C14 C15 0.4(5) . . . . ?
C11 C13 C14 C15 -176.8(3) . . . . ?
C3 C2 C1 C6 0.9(5) . . . . ?
C5 C6 C1 C2 0.4(5) . . . . ?
C7 C6 C1 C2 -178.5(3) . . . . ?
C2 C3 C4 C5 0.5(5) . . . . ?
Br C3 C4 C5 -179.4(2) . . . . ?
C9 N1 C25 C24 159.7(3) . . . . ?
C21 N1 C25 C24 -60.6(3) . . . . ?
C17 C16 C15 C14 -1.3(5) . . . . ?
C19 C16 C15 C14 179.1(3) . . . . ?
C13 C14 C15 C16 0.6(5) . . . . ?
C9 N1 C21 C22 -157.3(3) . . . . ?
C25 N1 C21 C22 62.3(4) . . . . ?
C1 C6 C5 C4 -1.3(5) . . . . ?
C7 C6 C5 C4 177.7(3) . . . . ?
C3 C4 C5 C6 0.9(5) . . . . ?
N1 C25 C24 C23 55.3(4) . . . . ?
N1 C21 C22 C23 -56.2(4) . . . . ?
C21 C22 C23 C24 51.2(5) . . . . ?
C25 C24 C23 C22 -51.8(5) . . . . ?

_refine_diff_density_max         0.388
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.051



