# Electronic Supplementary Material (ESI) for ChemComm.
# 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_compound9
_database_code_depnum_ccdc_archive 'CCDC 1886326'

_audit_update_record             
;
2018-12-19 deposited with the CCDC.
2019-01-30 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H25 N O2'
_chemical_formula_weight         323.42


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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21/c'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   9.4055(10)
_cell_length_b                   20.834(2)
_cell_length_c                   9.2746(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 107.844(3)
_cell_angle_gamma                90.00
_cell_volume                     1730.0(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    4924
_cell_measurement_theta_min      2.4761
_cell_measurement_theta_max      23.1527

_exptl_crystal_description       needle
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.06
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.242
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             696
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9721
_exptl_absorpt_correction_T_max  0.9953
_exptl_absorpt_process_details   SADABS

_exptl_special_details           ?

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  CCD
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            19854
_diffrn_reflns_av_R_equivalents  0.0806
_diffrn_reflns_av_sigmaI/netI    0.0572
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         1.95
_diffrn_reflns_theta_max         23.29
_reflns_number_total             2497
_reflns_number_gt                1668
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1000P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.038(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2497
_refine_ls_number_parameters     230
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0984
_refine_ls_R_factor_gt           0.0506
_refine_ls_wR_factor_ref         0.1471
_refine_ls_wR_factor_gt          0.1247
_refine_ls_goodness_of_fit_ref   0.962
_refine_ls_restrained_S_all      0.962
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
H1 H 0.757(3) 0.4997(14) 1.103(3) 0.057(9) Uiso 1 1 d . . .
N1 N 0.7939(2) 0.46835(11) 1.0628(3) 0.0477(7) Uani 1 1 d . . .
C2 C 0.8871(3) 0.42602(11) 1.1837(3) 0.0388(7) Uani 1 1 d . . .
C3 C 1.0359(3) 0.41388(12) 1.1552(3) 0.0413(7) Uani 1 1 d . . .
H3A H 1.0920 0.3821 1.2266 0.050 Uiso 1 1 calc R . .
H3B H 1.0935 0.4533 1.1717 0.050 Uiso 1 1 calc R . .
C4 C 1.0138(3) 0.39022(11) 0.9942(3) 0.0366(7) Uani 1 1 d . . .
H4 H 0.9948 0.4287 0.9305 0.044 Uiso 1 1 calc R . .
C5 C 0.8688(3) 0.34928(11) 0.9387(2) 0.0357(7) Uani 1 1 d . . .
H5 H 0.8834 0.3172 0.8673 0.043 Uiso 1 1 calc R . .
C6 C 0.7371(3) 0.39019(12) 0.8563(3) 0.0385(7) Uani 1 1 d . . .
C7 C 0.6466(3) 0.37328(13) 0.7130(3) 0.0464(7) Uani 1 1 d . . .
H7 H 0.6685 0.3354 0.6712 0.056 Uiso 1 1 calc R . .
C8 C 0.5268(3) 0.40869(16) 0.6285(3) 0.0561(8) Uani 1 1 d . . .
C9 C 0.4979(3) 0.46441(16) 0.6950(4) 0.0630(9) Uani 1 1 d . . .
H9 H 0.4179 0.4900 0.6419 0.076 Uiso 1 1 calc R . .
C10 C 0.5842(3) 0.48355(14) 0.8386(3) 0.0566(8) Uani 1 1 d . . .
H10 H 0.5609 0.5214 0.8797 0.068 Uiso 1 1 calc R . .
C11 C 0.7049(3) 0.44686(12) 0.9213(3) 0.0420(7) Uani 1 1 d . . .
C12 C 0.8047(3) 0.36132(11) 1.1823(3) 0.0384(7) Uani 1 1 d . . .
H12 H 0.6980 0.3715 1.1422 0.046 Uiso 1 1 calc R . .
C15A C 0.8357(3) 0.31395(11) 1.0679(2) 0.0350(6) Uani 1 1 d . . .
H13A H 0.7464 0.2875 1.0257 0.042 Uiso 1 1 calc R . .
H13B H 0.970(3) 0.2460(13) 1.083(3) 0.052 Uiso 1 1 d . . .
O13 O 0.95634(19) 0.27287(8) 1.14652(19) 0.0444(5) Uani 1 1 d . . .
C14 C 0.8242(3) 0.32957(13) 1.3350(3) 0.0472(7) Uani 1 1 d . . .
H14B H 0.7852 0.3583 1.3961 0.057 Uiso 1 1 calc R . .
H14A H 0.7641 0.2908 1.3184 0.057 Uiso 1 1 calc R . .
H14 H 1.010(3) 0.2890(13) 1.348(3) 0.071 Uiso 1 1 d . . .
O14 O 0.9737(2) 0.31310(9) 1.41894(19) 0.0518(6) Uani 1 1 d . . .
C21 C 0.9150(3) 0.46226(13) 1.3320(3) 0.0572(8) Uani 1 1 d . . .
H21B H 0.8224 0.4676 1.3540 0.086 Uiso 1 1 calc R . .
H21C H 0.9566 0.5036 1.3234 0.086 Uiso 1 1 calc R . .
H21A H 0.9836 0.4385 1.4122 0.086 Uiso 1 1 calc R . .
C41 C 1.1470(3) 0.35784(11) 0.9666(3) 0.0383(7) Uani 1 1 d . . .
C42 C 1.2635(3) 0.33075(14) 1.0775(3) 0.0565(8) Uani 1 1 d . . .
H42 H 1.2627 0.3318 1.1775 0.068 Uiso 1 1 calc R . .
C43 C 1.3817(3) 0.30197(16) 1.0438(4) 0.0710(9) Uani 1 1 d . . .
H43 H 1.4591 0.2838 1.1209 0.085 Uiso 1 1 calc R . .
C44 C 1.3855(4) 0.30015(15) 0.8986(4) 0.0688(10) Uani 1 1 d . . .
H44 H 1.4655 0.2810 0.8761 0.083 Uiso 1 1 calc R . .
C45 C 1.2716(4) 0.32656(15) 0.7859(4) 0.0657(9) Uani 1 1 d . . .
H45 H 1.2737 0.3254 0.6863 0.079 Uiso 1 1 calc R . .
C46 C 1.1536(3) 0.35487(13) 0.8196(3) 0.0521(8) Uani 1 1 d . . .
H46 H 1.0761 0.3725 0.7416 0.063 Uiso 1 1 calc R . .
C81 C 0.4306(4) 0.38828(17) 0.4742(3) 0.0830(11) Uani 1 1 d . . .
H81C H 0.3736 0.3511 0.4834 0.125 Uiso 1 1 calc R . .
H81B H 0.4927 0.3781 0.4123 0.125 Uiso 1 1 calc R . .
H81A H 0.3640 0.4226 0.4282 0.125 Uiso 1 1 calc R . .


_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 C11 1.397(3) . ?
N1 C2 1.483(3) . ?
C2 C21 1.519(3) . ?
C2 C3 1.523(3) . ?
C2 C12 1.553(3) . ?
C3 C4 1.525(3) . ?
C4 C41 1.512(3) . ?
C4 C5 1.556(3) . ?
C5 C6 1.505(3) . ?
C5 C15A 1.518(3) . ?
C6 C7 1.387(3) . ?
C6 C11 1.401(3) . ?
C7 C8 1.374(4) . ?
C8 C9 1.380(4) . ?
C8 C81 1.501(4) . ?
C9 C10 1.389(4) . ?
C10 C11 1.388(4) . ?
C12 C14 1.523(3) . ?
C12 C15A 1.541(3) . ?
C15A O13 1.430(3) . ?
C14 O14 1.424(3) . ?
C41 C42 1.374(4) . ?
C41 C46 1.385(3) . ?
C42 C43 1.381(4) . ?
C43 C44 1.359(4) . ?
C44 C45 1.362(4) . ?
C45 C46 1.375(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
C11 N1 C2 124.4(2) . . ?
N1 C2 C21 106.7(2) . . ?
N1 C2 C3 109.2(2) . . ?
C21 C2 C3 109.1(2) . . ?
N1 C2 C12 109.38(19) . . ?
C21 C2 C12 112.7(2) . . ?
C3 C2 C12 109.70(19) . . ?
C2 C3 C4 111.53(19) . . ?
C41 C4 C3 116.0(2) . . ?
C41 C4 C5 112.76(19) . . ?
C3 C4 C5 110.13(18) . . ?
C6 C5 C15A 109.84(18) . . ?
C6 C5 C4 111.03(18) . . ?
C15A C5 C4 112.07(18) . . ?
C7 C6 C11 118.5(2) . . ?
C7 C6 C5 120.7(2) . . ?
C11 C6 C5 120.8(2) . . ?
C8 C7 C6 124.4(3) . . ?
C7 C8 C9 115.9(3) . . ?
C7 C8 C81 122.7(3) . . ?
C9 C8 C81 121.4(3) . . ?
C8 C9 C10 122.2(3) . . ?
C11 C10 C9 120.7(3) . . ?
C10 C11 N1 119.8(3) . . ?
C10 C11 C6 118.3(3) . . ?
N1 C11 C6 121.9(2) . . ?
C14 C12 C15A 111.6(2) . . ?
C14 C12 C2 116.8(2) . . ?
C15A C12 C2 111.28(18) . . ?
O13 C15A C5 111.69(18) . . ?
O13 C15A C12 108.70(18) . . ?
C5 C15A C12 111.15(19) . . ?
O14 C14 C12 115.5(2) . . ?
C42 C41 C46 116.9(2) . . ?
C42 C41 C4 124.7(2) . . ?
C46 C41 C4 118.4(2) . . ?
C41 C42 C43 121.5(3) . . ?
C44 C43 C42 120.3(3) . . ?
C43 C44 C45 119.7(3) . . ?
C44 C45 C46 119.9(3) . . ?
C45 C46 C41 121.7(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
C11 N1 C2 C21 -158.5(2) . . . . ?
C11 N1 C2 C3 83.8(3) . . . . ?
C11 N1 C2 C12 -36.2(3) . . . . ?
N1 C2 C3 C4 -52.1(3) . . . . ?
C21 C2 C3 C4 -168.3(2) . . . . ?
C12 C2 C3 C4 67.8(2) . . . . ?
C2 C3 C4 C41 -162.1(2) . . . . ?
C2 C3 C4 C5 -32.5(3) . . . . ?
C41 C4 C5 C6 -136.4(2) . . . . ?
C3 C4 C5 C6 92.3(2) . . . . ?
C41 C4 C5 C15A 100.3(2) . . . . ?
C3 C4 C5 C15A -31.0(3) . . . . ?
C15A C5 C6 C7 -107.7(2) . . . . ?
C4 C5 C6 C7 127.8(2) . . . . ?
C15A C5 C6 C11 73.5(3) . . . . ?
C4 C5 C6 C11 -51.0(3) . . . . ?
C11 C6 C7 C8 0.5(4) . . . . ?
C5 C6 C7 C8 -178.3(2) . . . . ?
C6 C7 C8 C9 -0.2(4) . . . . ?
C6 C7 C8 C81 -179.4(2) . . . . ?
C7 C8 C9 C10 -0.1(4) . . . . ?
C81 C8 C9 C10 179.0(3) . . . . ?
C8 C9 C10 C11 0.3(4) . . . . ?
C9 C10 C11 N1 177.4(2) . . . . ?
C9 C10 C11 C6 0.0(4) . . . . ?
C2 N1 C11 C10 156.8(2) . . . . ?
C2 N1 C11 C6 -26.0(4) . . . . ?
C7 C6 C11 C10 -0.4(3) . . . . ?
C5 C6 C11 C10 178.4(2) . . . . ?
C7 C6 C11 N1 -177.7(2) . . . . ?
C5 C6 C11 N1 1.1(3) . . . . ?
N1 C2 C12 C14 -144.7(2) . . . . ?
C21 C2 C12 C14 -26.2(3) . . . . ?
C3 C2 C12 C14 95.6(2) . . . . ?
N1 C2 C12 C15A 85.6(2) . . . . ?
C21 C2 C12 C15A -155.9(2) . . . . ?
C3 C2 C12 C15A -34.1(3) . . . . ?
C6 C5 C15A O13 178.18(18) . . . . ?
C4 C5 C15A O13 -57.9(2) . . . . ?
C6 C5 C15A C12 -60.2(2) . . . . ?
C4 C5 C15A C12 63.7(2) . . . . ?
C14 C12 C15A O13 -37.1(3) . . . . ?
C2 C12 C15A O13 95.4(2) . . . . ?
C14 C12 C15A C5 -160.4(2) . . . . ?
C2 C12 C15A C5 -27.9(3) . . . . ?
C15A C12 C14 O14 69.1(3) . . . . ?
C2 C12 C14 O14 -60.5(3) . . . . ?
C3 C4 C41 C42 21.5(3) . . . . ?
C5 C4 C41 C42 -106.8(3) . . . . ?
C3 C4 C41 C46 -158.6(2) . . . . ?
C5 C4 C41 C46 73.1(3) . . . . ?
C46 C41 C42 C43 0.1(4) . . . . ?
C4 C41 C42 C43 -180.0(3) . . . . ?
C41 C42 C43 C44 0.3(5) . . . . ?
C42 C43 C44 C45 -0.4(5) . . . . ?
C43 C44 C45 C46 0.0(5) . . . . ?
C44 C45 C46 C41 0.4(4) . . . . ?
C42 C41 C46 C45 -0.5(4) . . . . ?
C4 C41 C46 C45 179.6(2) . . . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        23.29
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.187
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.040



_publcif_funding_html            
;
;
####################################################################### 
# 
# 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_compound6b
_database_code_depnum_ccdc_archive 'CCDC 1886668'
_audit_update_record             
;
2018-12-21 deposited with the CCDC.
2019-01-30 downloaded from the CCDC.
;


_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H20 Br N O3'
_chemical_formula_weight         414.29

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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'C 2/c'

loop_
_symmetry_equiv_pos_as_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                   30.809(2)
_cell_length_b                   7.0596(5)
_cell_length_c                   18.5420(14)
_cell_angle_alpha                90.00
_cell_angle_beta                 110.172(2)
_cell_angle_gamma                90.00
_cell_volume                     3785.5(5)
_cell_formula_units_Z            8
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9799
_cell_measurement_theta_min      2.2776
_cell_measurement_theta_max      24.1029

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.24
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.454
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1696
_exptl_absorpt_coefficient_mu    2.192
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4388
_exptl_absorpt_correction_T_max  0.6213
_exptl_absorpt_process_details   SADABS


_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker PHOTON CCC'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            48902
_diffrn_reflns_av_R_equivalents  0.0394
_diffrn_reflns_av_sigmaI/netI    0.0191
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         2.28
_diffrn_reflns_theta_max         24.27
_reflns_number_total             3039
_reflns_number_gt                2541
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1000P)²+0.0322P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0078(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3039
_refine_ls_number_parameters     242
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0933
_refine_ls_R_factor_gt           0.0787
_refine_ls_wR_factor_ref         0.2584
_refine_ls_wR_factor_gt          0.2498
_refine_ls_goodness_of_fit_ref   2.095
_refine_ls_restrained_S_all      2.095
_refine_ls_shift/su_max          0.014
_refine_ls_shift/su_mean         0.002

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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 1.03362(2) 0.73043(11) 0.38623(4) 0.0692(5) Uani 1 1 d . . .
C11 C 0.90012(17) 0.5131(7) 0.4253(3) 0.0383(12) Uani 1 1 d . . .
C8 C 0.98006(17) 0.6409(8) 0.4042(3) 0.0455(13) Uani 1 1 d . . .
C6 C 0.91742(18) 0.6957(7) 0.4491(3) 0.0381(12) Uani 1 1 d . . .
C10 C 0.92475(19) 0.3965(8) 0.3941(3) 0.0509(15) Uani 1 1 d . . .
H10 H 0.9141 0.2742 0.3794 0.061 Uiso 1 1 calc R . .
C2 C 0.82520(18) 0.5512(7) 0.4498(3) 0.0454(14) Uani 1 1 d . . .
C9 C 0.9660(2) 0.4586(8) 0.3837(3) 0.0533(15) Uani 1 1 d . . .
H9 H 0.9830 0.3782 0.3637 0.064 Uiso 1 1 calc R . .
C13 C 0.8846(2) 0.7377(7) 0.5565(4) 0.0479(15) Uani 1 1 d . . .
H13 H 0.9100 0.6487 0.5794 0.058 Uiso 1 1 calc R . .
C7 C 0.95668(19) 0.7564(7) 0.4372(3) 0.0402(13) Uani 1 1 d . . .
H7 H 0.9676 0.8784 0.4519 0.048 Uiso 1 1 calc R . .
C5 C 0.89302(19) 0.8304(7) 0.4866(3) 0.0414(13) Uani 1 1 d . . .
H5 H 0.9119 0.9443 0.5037 0.050 Uiso 1 1 calc R . .
C3 C 0.8128(2) 0.7264(8) 0.3900(5) 0.0629(19) Uani 1 1 d . . .
H3 H 0.8176 0.6827 0.3432 0.075 Uiso 1 1 calc R . .
C4 C 0.84777(18) 0.8840(7) 0.4242(3) 0.0427(13) Uani 1 1 d . . .
C12 C 0.8387(2) 0.6189(9) 0.5294(4) 0.0679(19) Uani 1 1 d . . .
H12A H 0.8424 0.5105 0.5632 0.081 Uiso 1 1 calc R . .
H12B H 0.8139 0.6962 0.5345 0.081 Uiso 1 1 calc R . .
C31 C 0.7671(3) 0.7964(10) 0.3681(4) 0.0626(19) Uani 1 1 d . . .
C32 C 0.6925(2) 0.8112(13) 0.2748(4) 0.077(2) Uani 1 1 d . . .
H32A H 0.6774 0.7525 0.3065 0.115 Uiso 1 1 calc R . .
H32B H 0.6775 0.7734 0.2224 0.115 Uiso 1 1 calc R . .
H32C H 0.6908 0.9464 0.2787 0.115 Uiso 1 1 calc R . .
O31 O 0.75313(19) 0.8976(8) 0.4128(3) 0.0941(18) Uani 1 1 d . . .
O32 O 0.73938(19) 0.7544(6) 0.2997(3) 0.0793(17) Uani 1 1 d . . .
O4 O 0.84069(14) 1.0382(5) 0.3938(2) 0.0586(11) Uani 1 1 d . . .
C41 C 0.88575(19) 0.8799(8) 0.6176(3) 0.0470(14) Uani 1 1 d . . .
C42 C 0.8525(2) 1.0231(9) 0.6038(3) 0.0610(17) Uani 1 1 d . . .
H42 H 0.8295 1.0328 0.5557 0.073 Uiso 1 1 calc R . .
C43 C 0.8534(3) 1.1511(10) 0.6613(4) 0.072(2) Uani 1 1 d . . .
H43 H 0.8305 1.2429 0.6519 0.086 Uiso 1 1 calc R . .
C44 C 0.8876(3) 1.1431(11) 0.7314(4) 0.079(2) Uani 1 1 d . . .
H44 H 0.8887 1.2320 0.7690 0.095 Uiso 1 1 calc R . .
C46 C 0.9194(2) 0.8718(10) 0.6890(4) 0.0633(17) Uani 1 1 d . . .
H46 H 0.9418 0.7774 0.6996 0.076 Uiso 1 1 calc R . .
N1 N 0.86059(15) 0.4454(6) 0.4348(3) 0.0462(12) Uani 1 1 d . . .
C21 C 0.7827(2) 0.4201(8) 0.4312(5) 0.071(2) Uani 1 1 d . . .
H21A H 0.7735 0.3800 0.3786 0.106 Uiso 1 1 calc R . .
H21B H 0.7577 0.4875 0.4392 0.106 Uiso 1 1 calc R . .
H21C H 0.7904 0.3113 0.4642 0.106 Uiso 1 1 calc R . .
C45 C 0.9205(3) 1.0026(11) 0.7460(4) 0.081(2) Uani 1 1 d . . .
H45 H 0.9436 0.9949 0.7941 0.097 Uiso 1 1 calc R . .
H1 H 0.854(3) 0.293(12) 0.425(5) 0.09(3) 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
Br1 C8 1.900(5) . ?
C11 C10 1.375(7) . ?
C11 N1 1.375(6) . ?
C11 C6 1.406(7) . ?
C8 C9 1.369(8) . ?
C8 C7 1.365(8) . ?
C6 C7 1.371(8) . ?
C6 C5 1.522(8) . ?
C10 C9 1.419(8) . ?
C2 N1 1.426(7) . ?
C2 C12 1.469(8) . ?
C2 C21 1.543(7) . ?
C2 C3 1.617(9) . ?
C13 C41 1.504(8) . ?
C13 C5 1.552(8) . ?
C13 C12 1.570(8) . ?
C5 C4 1.521(8) . ?
C3 C31 1.411(10) . ?
C3 C4 1.527(8) . ?
C4 O4 1.210(6) . ?
C31 O31 1.277(9) . ?
C31 O32 1.295(9) . ?
C32 O32 1.415(9) . ?
C41 C46 1.373(8) . ?
C41 C42 1.399(8) . ?
C42 C43 1.391(9) . ?
C43 C44 1.363(10) . ?
C44 C45 1.376(11) . ?
C46 C45 1.395(10) . ?

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
C10 C11 N1 119.2(4) . . ?
C10 C11 C6 118.4(5) . . ?
N1 C11 C6 122.4(5) . . ?
C9 C8 C7 121.4(5) . . ?
C9 C8 Br1 118.3(4) . . ?
C7 C8 Br1 120.3(4) . . ?
C7 C6 C11 119.8(5) . . ?
C7 C6 C5 118.7(5) . . ?
C11 C6 C5 121.5(5) . . ?
C11 C10 C9 121.5(5) . . ?
N1 C2 C12 113.4(5) . . ?
N1 C2 C21 106.8(4) . . ?
C12 C2 C21 110.1(5) . . ?
N1 C2 C3 106.4(5) . . ?
C12 C2 C3 111.0(5) . . ?
C21 C2 C3 108.8(5) . . ?
C8 C9 C10 117.7(5) . . ?
C41 C13 C5 112.3(4) . . ?
C41 C13 C12 112.5(5) . . ?
C5 C13 C12 110.5(5) . . ?
C8 C7 C6 121.1(5) . . ?
C4 C5 C6 106.0(4) . . ?
C4 C5 C13 111.5(5) . . ?
C6 C5 C13 111.7(4) . . ?
C31 C3 C4 110.8(5) . . ?
C31 C3 C2 116.3(6) . . ?
C4 C3 C2 107.8(5) . . ?
O4 C4 C5 123.3(5) . . ?
O4 C4 C3 118.3(5) . . ?
C5 C4 C3 117.7(5) . . ?
C2 C12 C13 114.0(5) . . ?
O31 C31 O32 120.4(7) . . ?
O31 C31 C3 122.3(7) . . ?
O32 C31 C3 117.3(8) . . ?
C31 O32 C32 120.7(7) . . ?
C46 C41 C42 117.9(6) . . ?
C46 C41 C13 120.9(6) . . ?
C42 C41 C13 121.2(5) . . ?
C43 C42 C41 120.6(6) . . ?
C44 C43 C42 120.6(7) . . ?
C43 C44 C45 119.5(6) . . ?
C41 C46 C45 121.2(7) . . ?
C11 N1 C2 127.8(4) . . ?
C44 C45 C46 120.2(7) . . ?

_diffrn_measured_fraction_theta_max 0.990
_diffrn_reflns_theta_full        24.27
_diffrn_measured_fraction_theta_full 0.990
_refine_diff_density_max         1.376
_refine_diff_density_min         -0.574
_refine_diff_density_rms         0.102
