# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# 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_98freeB
_database_code_depnum_ccdc_archive 'CCDC 2307637'
loop_
_audit_author_name
_audit_author_address
'Giovanni Macetti'
;Universita degli Studi di Milano
Italy
;
_audit_update_record             
;
2023-11-13 deposited with the CCDC.	2024-02-14 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_RINTA01_98freeB             
;
PROBLEM: The value of Rint is greater than 0.18
RESPONSE: The investigated crystal was a poorly diffracting needle and the    system was also twinned, with at least two different crystalline phases.    Unfortunately, the molecule is difficult to crystallize and these data     are the best we have obtained. However, since the scope of this    data collection was to determine the atom-atom connectivity and the    absolute stereogenic configuration, we believe that the data is    sufficiently reliable, although the Rint value is not very good.
;
_vrf_PLAT020_98freeB             
;
PROBLEM: The Value of Rint is Greater Than 0.12 .........      0.182 Report
RESPONSE: The investigated crystal was a poorly diffracting needle and the    system was also twinned, with at least two different crystalline phases.    Unfortunately, the molecule is difficult to crystallize and these data     are the best we have obtained. However, since the scope of this    data collection was to determine the atom-atom connectivity and the    absolute stereogenic configuration, we believe that the data are    sufficiently good, although the Rint value is not very good.
;
_vrf_PLAT082_98freeB             
;
PROBLEM: High R1 Value ..................................       0.16 Report
RESPONSE: The overall quality of the collected data is poor because the crystal    was poorly diffracting and twinning was present. However, although the     agreement factor R1 is quite high, we were able to refine the crystal    structure without problems and the obtained geometry does not show           distorsions or unexpected features. Since the scope of this data       collection was to determine the chemical connectivity and the absolute     stereochemical configuration of the studied molecule, we believe that           this R-factor bad agreement is not detrimental for the quality of the    obtained stucture.
;
_vrf_PLAT084_98freeB             
;
PROBLEM: High wR2 Value (i.e. > 0.25) ...................       0.45 Report
RESPONSE: The overall quality of the collected data is poor because the crystal    was poorly diffracting and twinning was present. However, although the     agreement factor wR2 was quite high, we were able to refine the crystal    structure without problems and the obtained geometry does not show           distorsions or unexpected features. Since the scope of this data       collection was to determine the chemical connectivity and the absolute     stereochemical configuration of the studied molecule, we believe that           this R-factor bad agreement is not detrimental for the quality of the    obtained stucture.
;
_vrf_PLAT097_98freeB             
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       0.90 eA-3
RESPONSE: The residual density is larger because the quality of the measured    sample is poor, and also there is the presence of twinning.    However, since the scope of this data collection was to determine           the atom-atom connectivity and the absolute stereogenic    configuration, we believe that the quality of the data is sufficient    in order to have reliable results.
;
_vrf_PLAT934_98freeB             
;
PROBLEM: Number of (Iobs-Icalc)/Sigma(W) > 10 Outliers ..          2 Check
RESPONSE: This discrepancy between observed and calculated structure factors    are related to the presence of twinning in the analyzed sample and,    therefore, to the overall poor quality of the collected data. We did not    remove these data from the refinement to avoid any possible bias.
;
_vrf_DIFMN02_98freeB             
;
PROBLEM: The minimum difference density is < -0.1*ZMAX*0.75
RESPONSE: The residual electron density is not adequate because, unfortunately, the quality of the measured sample is poor and also there is the presence of twinning. However, since the scope of this data collection was to determine the atom-atom connectivity and the absolute stereogenic configuration, we believe that the data is sufficiently reliable.
;
_vrf_DIFMN03_98freeB             
;
PROBLEM: The minimum difference density is < -0.1*ZMAX*0.75
RESPONSE: The residual electron density is not adequate because, unfortunately, the quality of the measured sample was poor. Moreover, the crystal is also twinned. However, since the scope of this data collection was to determine the atom-atom connectivity and the absolute stereogenic configuration, we believe that the data are sufficiently good and we were able to detect them in a confident way.
;
_vrf_DIFMX02_98freeB             
;
PROBLEM: The maximum difference density is > 0.1*ZMAX*0.75
RESPONSE: The residual electron density is not adequate because, unfortunately, the quality of the measured sample was poor and there is also the presence of twinning. However, since the scope of this data collection was to determine the atom-atom connectivity and the absolute stereogenic configuration, we believe that the data are sufficiently good and we were able to detect them in a confindent way.
;
_vrf_PLAT098_98freeB             
;
PROBLEM: Large Reported Min.  (Negative) Residual Density      -0.65 eA-3
RESPONSE: The residual density is larger because the quality of the measured    sample is poor and also there is the presence of twinning.    However, since the scope of this data collection was to determine           the atom-atom connectivity and the absolute stereogenic    configuration, we believe that the quality of the data is sufficient    to obtain reliable results.
;
_vrf_PLAT112_98freeB             
;
PROBLEM: ADDSYM Detects New (Pseudo) Symm. Elem       a/2         92 %Fit
RESPONSE: The observed new element is only a pseudo-symmetry element.    We evaluated the possibility of chosing an higher-symmetry space group,    but we were not able to find any possible transformation matrix to operate    this change. Moreover, since the maximum deviation for non-H atoms is 0.43    Angstrom, and the overall data quality is poor, we preferred to stick with           this description because we believe we can not confidently conclude    that the presence of this pseudo-symmetry element is something real.
;
_vrf_PLAT340_98freeB             
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.00821 Ang.
RESPONSE: The low precision on C-C bonds is due to the overall poor quality of    the used dataset. However, since we were interested in detecting the    chemical connectivity and the absolute configuration of the    studied molecule, we believe that this small discrepancies do not    negatively affect the obtained results.
;
_vrf_PLAT906_98freeB             
;
PROBLEM: Large K Value in the Analysis of Variance ......     44.041 Check
RESPONSE: These K values are limited to diffraction data with very weak    intensities. This is because the crystal is           poorly diffracting and also the overall quality of the sample is           poor. However, the determination of the chemical connectivity and    the determination of the absolute sterochemical configuration is only     marginally affected and we believe the final structure can be    considered reliable.
;
_vrf_PLAT906_98freeB_2           
;
PROBLEM: Large K Value in the Analysis of Variance ......      8.500 Check
RESPONSE: These K values are limited to diffraction data with very weak    intensities. This is because the crystal is           poorly diffracting and also the overall quality of the sample is           poor. However, the determination of the chemical connectivity and    the determination of the absolute sterochemical configuration is only     marginally affected and we believe the final structure can be    considered reliable.
;
_vrf_PLAT906_98freeB_3           
;
PROBLEM: Large K Value in the Analysis of Variance ......      4.015 Check
RESPONSE: These K values are limited to diffraction data with very weak    intensities. This is because the crystal is           poorly diffracting and also the overall quality of the sample is           poor. However, the determination of the chemical connectivity and    the determination of the absolute sterochemical configuration is only     marginally affected and we believe the final structure can be    considered reliable.
;
_vrf_PLAT910_98freeB             
;
PROBLEM: Missing # of FCF Reflection(s) Below Theta(Min).          8 Note
RESPONSE: This is a consequence of the distance of the detector from the    beamstop. The detector was set as close as possible to the sample to collect    the maximum diffracted intensities. For this reason, some low-angle    reflection was covered by the beamstop.
;
_vrf_PLAT975_98freeB             
;
PROBLEM: Check Calcd Resid. Dens.  0.94Ang From O1A     .       0.99 eA-3
RESPONSE: The residual density is larger because the quality of the measured    sample is poor and also there is the presence of twinning.    However, since the scope of this data collection was to determine           the atom-atom connectivity and the absolute stereogenic    configuration, we believe that the quality of the data is sufficient.
;
_vrf_PLAT975_98freeB_2           
;
PROBLEM: Check Calcd Resid. Dens.  1.03Ang From N1A     .       0.98 eA-3
RESPONSE: The residual density is larger because the quality of the measured    sample is poor and also there is the presence of twinning.    However, since the scope of this data collection was to determine           the atom-atom connectivity and the absolute stereogenic    configuration, we believe that the quality of the data is sufficient.
;
_vrf_PLAT975_98freeB_3           
;
PROBLEM: Check Calcd Resid. Dens.  0.96Ang From O1B     .       0.93 eA-3
RESPONSE: The residual density is larger because the quality of the measured    sample is poor and also there is the presence of twinning.    However, since the scope of this data collection was to determine           the atom-atom connectivity and the absolute stereogenic    configuration, we believe that the quality of the data is sufficient.
;
_vrf_PLAT975_98freeB_4           
;
PROBLEM: Check Calcd Resid. Dens.  0.82Ang From N1B     .       0.75 eA-3
RESPONSE: The residual density is larger because the quality of the measured    sample is poor and also there is the presence of twinning.    However, since the scope of this data collection was to determine           the atom-atom connectivity and the absolute stereogenic    configuration, we believe that the quality of the data is sufficient.
;
_vrf_PLAT977_98freeB             
;
PROBLEM: Check Negative Difference Density on H9AB      .      -0.58 eA-3
RESPONSE: These negative difference density on the hydrogen atoms positions    are due to the poor data quality of the collected sample. This is    not a problem because the hydrogen atoms have been located using    the HFIX command of SHELX, i.e. geometrical restraints were applied.
;
_vrf_PLAT977_98freeB_2           
;
PROBLEM: Check Negative Difference Density on H9BA      .      -0.52 eA-3
RESPONSE: These negative difference density on the hydrogen atoms positions    are due to the poor data quality of the collected sample. This is    not a problem because the hydrogen atoms have been located using    the HFIX command of SHELX, i.e. geometrical restraints were applied.
;
_vrf_PLAT977_98freeB_3           
;
PROBLEM: Check Negative Difference Density on H16B      .      -0.31 eA-3
RESPONSE: These negative difference density on the hydrogen atoms positions    are due to the poor data quality of the collected sample. This is    not a problem because the hydrogen atoms have been located using    the HFIX command of SHELX, i.e. geometrical restraints were applied.
;
_audit_creation_date             2023-07-20
_audit_creation_method           SHELXL-2018/3
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4.5
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic


#------------------ CHEMICAL INFORMATION ------------------------------------#  
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          440-442
_chemical_formula_moiety         'C23 H19 N O'
_chemical_formula_sum            'C46 H38 N2 O2'
_chemical_formula_weight         650.78

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'

_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                   11.5430(6)
_cell_length_b                   11.9861(9)
_cell_length_c                   13.8670(9)
_cell_angle_alpha                84.966(6)
_cell_angle_beta                 76.217(5)
_cell_angle_gamma                62.126(6)
_cell_volume                     1646.5(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    8484
_cell_measurement_theta_min      2.7750
_cell_measurement_theta_max      31.0060

_exptl_crystal_description       needle
_exptl_crystal_colour            'translucent pale colourless'
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_F_000             688
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          1.0
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_exptl_absorpt_coefficient_mu    0.080
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.39224
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_monochromator  mirror
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            HyPix
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -20.00  31.00   0.50   60.00    --   -0.21-100.00  98.00  102
  2  ω    -21.00  29.00   0.50   60.00    --   -0.21 -99.00  30.00  100
  3  ω    -20.00  54.00   0.50   60.00    --   -0.21  77.00-120.00  148
  4  ω    -22.00  30.00   0.50   60.00    --   -0.21 -99.00 150.00  104
  5  ω    -23.00  30.00   0.50   60.00    --   -0.21 -99.00 -90.00  106
  6  ω    -19.00  72.00   0.50   60.00    --   -0.21  77.00-180.00  182
  7  ω    -25.00  12.00   0.50   60.00    --    4.00 -30.00-156.30   74
  8  ω    -60.00  12.00   0.50   60.00    --    4.00 -29.00  46.78  144
  9  ω    -61.00 -29.00   0.50   60.00    --    4.00 -30.00-156.30   64
 10  ω    -11.00  35.00   0.50   60.00    --   -4.00  18.00-106.66   92
 11  ω    -11.00  53.00   0.50   60.00    --   -4.00  15.00 108.95  128
 12  ω    -11.00  68.00   0.50   60.00    --   -4.00  14.00 163.81  158
 13  ω    -12.00   6.50   0.50   60.00    --   -4.00  24.00 -12.78   37
;
_diffrn_reflns_number            39576
_diffrn_reflns_av_unetI/netI     0.1283
_diffrn_reflns_av_R_equivalents  0.1816
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.788
_diffrn_reflns_theta_max         31.303
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.798
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.798
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.798
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             8604
_reflns_number_gt                5996
_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 1.171.42.90a (Rigaku OD, 2023)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_structure_solution    'SHELXL-2014/4 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/4 (Sheldrick, 2014)'
_computing_molecular_graphics    'Mercury 4.0 (Macrae, 2020)'
_computing_publication_material  ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1912P)²+10.3480P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .

_refine_ls_number_reflns         8604
_refine_ls_number_parameters     451
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1936
_refine_ls_R_factor_gt           0.1597
_refine_ls_wR_factor_ref         0.4461
_refine_ls_wR_factor_gt          0.4266
_refine_ls_goodness_of_fit_ref   1.125
_refine_ls_restrained_S_all      1.125
_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
O1A O 0.7107(3) 0.4176(3) 0.6104(3) 0.0185(7) Uani 1 1 d . . . . .
N1A N 0.5657(4) 0.5998(4) 0.5469(3) 0.0183(8) Uani 1 1 d . . . . .
H1NA H 0.625497 0.611636 0.500591 0.022 Uiso 1 1 calc R U . . .
C1A C 0.5964(5) 0.5032(4) 0.6105(3) 0.0146(9) Uani 1 1 d . . . . .
C2A C 0.4264(5) 0.6788(5) 0.5641(4) 0.0178(9) Uani 1 1 d . . . . .
C3A C 0.3565(5) 0.7869(5) 0.5159(4) 0.0211(10) Uani 1 1 d . . . . .
H3A H 0.401735 0.819055 0.463779 0.025 Uiso 1 1 calc R U . . .
C4A C 0.2162(6) 0.8473(5) 0.5470(4) 0.0240(11) Uani 1 1 d . . . . .
H4A H 0.165327 0.921934 0.515234 0.029 Uiso 1 1 calc R U . . .
C5A C 0.1495(5) 0.8010(5) 0.6231(4) 0.0219(10) Uani 1 1 d . . . . .
H5A H 0.054025 0.843225 0.641827 0.026 Uiso 1 1 calc R U . . .
C6A C 0.2218(5) 0.6926(5) 0.6722(4) 0.0201(10) Uani 1 1 d . . . . .
H6A H 0.176637 0.661276 0.725095 0.024 Uiso 1 1 calc R U . . .
C7A C 0.3607(5) 0.6317(5) 0.6423(4) 0.0173(9) Uani 1 1 d . . . . .
C8A C 0.4668(5) 0.5190(5) 0.6780(3) 0.0163(9) Uani 1 1 d . . . . .
C9A C 0.4547(5) 0.4015(5) 0.7173(4) 0.0201(10) Uani 1 1 d . . . . .
H9AA H 0.368877 0.400161 0.719880 0.024 Uiso 1 1 calc R U . . .
H9AB H 0.535836 0.318855 0.700976 0.024 Uiso 1 1 calc R U . . .
C10A C 0.4541(5) 0.4878(5) 0.7886(4) 0.0194(10) Uani 1 1 d . . . . .
H10A H 0.363883 0.541040 0.831961 0.023 Uiso 1 1 calc R U . . .
C11A C 0.5709(5) 0.4492(5) 0.8370(4) 0.0208(10) Uani 1 1 d . . . . .
H11A H 0.565018 0.525938 0.863952 0.025 Uiso 1 1 calc R U . . .
H11B H 0.655436 0.410941 0.785409 0.025 Uiso 1 1 calc R U . . .
C12A C 0.5782(5) 0.3568(5) 0.9197(4) 0.0192(10) Uani 1 1 d . . . . .
C13A C 0.6849(5) 0.3124(5) 0.9674(4) 0.0232(11) Uani 1 1 d . . . . .
H13A H 0.749308 0.343154 0.948700 0.028 Uiso 1 1 calc R U . . .
C14A C 0.6989(5) 0.2248(5) 1.0412(4) 0.0224(11) Uani 1 1 d . . . . .
H14A H 0.773049 0.196106 1.071753 0.027 Uiso 1 1 calc R U . . .
C15A C 0.6060(5) 0.1771(5) 1.0721(4) 0.0188(10) Uani 1 1 d . . . . .
C16A C 0.4971(5) 0.2242(5) 1.0268(4) 0.0217(10) Uani 1 1 d . . . . .
H16A H 0.431285 0.195449 1.047042 0.026 Uiso 1 1 calc R U . . .
C17A C 0.4829(5) 0.3130(5) 0.9522(4) 0.0217(10) Uani 1 1 d . . . . .
H17A H 0.407241 0.343931 0.923035 0.026 Uiso 1 1 calc R U . . .
C18A C 0.6238(5) 0.0793(5) 1.1478(4) 0.0186(10) Uani 1 1 d . . . . .
C19A C 0.6832(5) 0.0741(5) 1.2262(4) 0.0210(10) Uani 1 1 d . . . . .
H19A H 0.712700 0.134896 1.231088 0.025 Uiso 1 1 calc R U . . .
C20A C 0.6998(5) -0.0180(5) 1.2966(4) 0.0241(11) Uani 1 1 d . . . . .
H20A H 0.741430 -0.020492 1.348688 0.029 Uiso 1 1 calc R U . . .
C21A C 0.6559(5) -0.1071(5) 1.2918(4) 0.0234(11) Uani 1 1 d . . . . .
H21A H 0.666386 -0.169777 1.340657 0.028 Uiso 1 1 calc R U . . .
C22A C 0.5965(5) -0.1031(5) 1.2145(4) 0.0254(11) Uani 1 1 d . . . . .
H22A H 0.566433 -0.163567 1.210305 0.030 Uiso 1 1 calc R U . . .
C23A C 0.5810(5) -0.0114(5) 1.1435(4) 0.0239(11) Uani 1 1 d . . . . .
H23A H 0.540567 -0.010075 1.090936 0.029 Uiso 1 1 calc R U . . .
O1B O 0.7770(3) 0.6009(3) 0.3954(3) 0.0188(7) Uani 1 1 d . . . . .
N1B N 0.9214(4) 0.4138(4) 0.4536(3) 0.0165(8) Uani 1 1 d . . . . .
H1NB H 0.862105 0.403017 0.501265 0.020 Uiso 1 1 calc R U . . .
C1B C 0.8910(5) 0.5125(4) 0.3924(3) 0.0147(9) Uani 1 1 d . . . . .
C2B C 1.0594(5) 0.3309(5) 0.4316(3) 0.0164(9) Uani 1 1 d . . . . .
C3B C 1.1286(5) 0.2171(5) 0.4751(4) 0.0189(10) Uani 1 1 d . . . . .
H3B H 1.083106 0.184431 0.526511 0.023 Uiso 1 1 calc R U . . .
C4B C 1.2677(5) 0.1528(5) 0.4401(4) 0.0229(11) Uani 1 1 d . . . . .
H4B H 1.318049 0.075539 0.469316 0.027 Uiso 1 1 calc R U . . .
C5B C 1.3345(5) 0.1987(5) 0.3639(4) 0.0228(10) Uani 1 1 d . . . . .
H5B H 1.429345 0.152591 0.341561 0.027 Uiso 1 1 calc R U . . .
C6B C 1.2632(5) 0.3126(5) 0.3196(4) 0.0206(10) Uani 1 1 d . . . . .
H6B H 1.308773 0.343949 0.267097 0.025 Uiso 1 1 calc R U . . .
C7B C 1.1248(5) 0.3787(5) 0.3538(4) 0.0171(9) Uani 1 1 d . . . . .
C8B C 1.0200(5) 0.4973(5) 0.3239(3) 0.0162(9) Uani 1 1 d . . . . .
C9B C 1.0326(5) 0.6166(5) 0.2933(4) 0.0180(9) Uani 1 1 d . . . . .
H9BA H 0.952651 0.698554 0.315076 0.022 Uiso 1 1 calc R U . . .
H9BB H 1.119775 0.614920 0.291027 0.022 Uiso 1 1 calc R U . . .
C10B C 1.0277(5) 0.5403(5) 0.2164(4) 0.0181(10) Uani 1 1 d . . . . .
H10B H 1.116343 0.489815 0.170183 0.022 Uiso 1 1 calc R U . . .
C11B C 0.9081(5) 0.5863(5) 0.1698(4) 0.0192(10) Uani 1 1 d . . . . .
H11C H 0.825190 0.632540 0.221259 0.023 Uiso 1 1 calc R U . . .
H11D H 0.904476 0.512083 0.147250 0.023 Uiso 1 1 calc R U . . .
C12B C 0.9093(5) 0.6719(5) 0.0823(4) 0.0175(9) Uani 1 1 d . . . . .
C13B C 0.8672(5) 0.6609(5) -0.0007(4) 0.0202(10) Uani 1 1 d . . . . .
H13B H 0.844573 0.594897 -0.004391 0.024 Uiso 1 1 calc R U . . .
C14B C 0.8575(5) 0.7438(5) -0.0781(4) 0.0193(10) Uani 1 1 d . . . . .
H14B H 0.828449 0.733603 -0.133824 0.023 Uiso 1 1 calc R U . . .
C15B C 0.8895(5) 0.8419(4) -0.0754(4) 0.0164(9) Uani 1 1 d . . . . .
C16B C 0.9331(5) 0.8520(5) 0.0081(4) 0.0210(10) Uani 1 1 d . . . . .
H16B H 0.955153 0.918280 0.012239 0.025 Uiso 1 1 calc R U . . .
C17B C 0.9447(5) 0.7680(5) 0.0844(4) 0.0205(10) Uani 1 1 d . . . . .
H17B H 0.977225 0.775762 0.138960 0.025 Uiso 1 1 calc R U . . .
C18B C 0.8721(5) 0.9370(5) -0.1544(4) 0.0179(9) Uani 1 1 d . . . . .
C19B C 0.7745(5) 0.9680(5) -0.2088(4) 0.0236(11) Uani 1 1 d . . . . .
H19B H 0.719391 0.926917 -0.195822 0.028 Uiso 1 1 calc R U . . .
C20B C 0.7566(6) 1.0578(6) -0.2815(4) 0.0270(12) Uani 1 1 d . . . . .
H20B H 0.689876 1.077386 -0.318124 0.032 Uiso 1 1 calc R U . . .
C21B C 0.8351(5) 1.1190(5) -0.3009(4) 0.0226(11) Uani 1 1 d . . . . .
H21B H 0.821330 1.182112 -0.349572 0.027 Uiso 1 1 calc R U . . .
C22B C 0.9342(6) 1.0876(5) -0.2488(4) 0.0230(11) Uani 1 1 d . . . . .
H22B H 0.989360 1.128689 -0.262499 0.028 Uiso 1 1 calc R U . . .
C23B C 0.9538(5) 0.9965(5) -0.1766(4) 0.0203(10) Uani 1 1 d . . . . .
H23 H 1.023197 0.974667 -0.142109 0.024 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
O1A C1A 1.235(6) . ?
N1A C1A 1.352(6) . ?
N1A C2A 1.404(6) . ?
C1A C8A 1.500(6) . ?
C2A C3A 1.380(7) . ?
C2A C7A 1.404(7) . ?
C3A C4A 1.400(8) . ?
C4A C5A 1.387(8) . ?
C5A C6A 1.397(7) . ?
C6A C7A 1.385(7) . ?
C7A C8A 1.481(7) . ?
C8A C9A 1.521(7) . ?
C8A C10A 1.536(7) . ?
C9A C10A 1.490(7) . ?
C10A C11A 1.509(7) . ?
C11A C12A 1.512(7) . ?
C12A C17A 1.397(7) . ?
C12A C13A 1.398(7) . ?
C13A C14A 1.381(7) . ?
C14A C15A 1.404(7) . ?
C15A C16A 1.394(7) . ?
C15A C18A 1.477(7) . ?
C16A C17A 1.398(7) . ?
C18A C23A 1.399(7) . ?
C18A C19A 1.400(7) . ?
C19A C20A 1.383(7) . ?
C20A C21A 1.391(8) . ?
C21A C22A 1.390(8) . ?
C22A C23A 1.386(7) . ?
O1B C1B 1.238(6) . ?
N1B C1B 1.349(6) . ?
N1B C2B 1.400(6) . ?
C1B C8B 1.502(7) . ?
C2B C3B 1.388(6) . ?
C2B C7B 1.404(7) . ?
C3B C4B 1.395(7) . ?
C4B C5B 1.385(8) . ?
C5B C6B 1.400(7) . ?
C6B C7B 1.388(7) . ?
C7B C8B 1.479(7) . ?
C8B C9B 1.517(7) . ?
C8B C10B 1.529(6) . ?
C9B C10B 1.492(7) . ?
C10B C11B 1.509(6) . ?
C11B C12B 1.521(6) . ?
C12B C13B 1.389(7) . ?
C12B C17B 1.396(7) . ?
C13B C14B 1.385(7) . ?
C14B C15B 1.394(7) . ?
C15B C16B 1.404(7) . ?
C15B C18B 1.487(6) . ?
C16B C17B 1.380(7) . ?
C18B C19B 1.393(7) . ?
C18B C23B 1.395(7) . ?
C19B C20B 1.385(7) . ?
C20B C21B 1.380(8) . ?
C21B C22B 1.384(8) . ?
C22B C23B 1.390(7) . ?

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
C1A N1A C2A 111.6(4) . . ?
O1A C1A N1A 125.4(4) . . ?
O1A C1A C8A 127.4(4) . . ?
N1A C1A C8A 107.2(4) . . ?
C3A C2A N1A 128.9(5) . . ?
C3A C2A C7A 121.9(5) . . ?
N1A C2A C7A 109.3(4) . . ?
C2A C3A C4A 117.2(5) . . ?
C5A C4A C3A 121.7(5) . . ?
C4A C5A C6A 120.4(5) . . ?
C7A C6A C5A 118.6(5) . . ?
C6A C7A C2A 120.2(5) . . ?
C6A C7A C8A 133.0(5) . . ?
C2A C7A C8A 106.8(4) . . ?
C7A C8A C1A 105.1(4) . . ?
C7A C8A C9A 125.2(4) . . ?
C1A C8A C9A 118.6(4) . . ?
C7A C8A C10A 121.7(4) . . ?
C1A C8A C10A 122.8(4) . . ?
C9A C8A C10A 58.3(3) . . ?
C10A C9A C8A 61.3(3) . . ?
C9A C10A C11A 121.3(5) . . ?
C9A C10A C8A 60.3(3) . . ?
C11A C10A C8A 120.8(4) . . ?
C10A C11A C12A 114.6(4) . . ?
C17A C12A C13A 117.4(5) . . ?
C17A C12A C11A 123.5(4) . . ?
C13A C12A C11A 119.0(4) . . ?
C14A C13A C12A 121.4(5) . . ?
C13A C14A C15A 121.5(5) . . ?
C16A C15A C14A 117.2(5) . . ?
C16A C15A C18A 121.2(5) . . ?
C14A C15A C18A 121.6(4) . . ?
C15A C16A C17A 121.3(5) . . ?
C12A C17A C16A 121.1(5) . . ?
C23A C18A C19A 117.7(4) . . ?
C23A C18A C15A 120.8(5) . . ?
C19A C18A C15A 121.5(4) . . ?
C20A C19A C18A 121.1(5) . . ?
C19A C20A C21A 120.6(5) . . ?
C22A C21A C20A 119.0(5) . . ?
C23A C22A C21A 120.4(5) . . ?
C22A C23A C18A 121.2(5) . . ?
C1B N1B C2B 111.3(4) . . ?
O1B C1B N1B 125.4(4) . . ?
O1B C1B C8B 126.9(4) . . ?
N1B C1B C8B 107.7(4) . . ?
C3B C2B N1B 128.6(5) . . ?
C3B C2B C7B 122.0(5) . . ?
N1B C2B C7B 109.4(4) . . ?
C2B C3B C4B 117.2(5) . . ?
C5B C4B C3B 121.7(5) . . ?
C4B C5B C6B 120.5(5) . . ?
C7B C6B C5B 118.8(5) . . ?
C6B C7B C2B 119.8(5) . . ?
C6B C7B C8B 133.2(5) . . ?
C2B C7B C8B 107.0(4) . . ?
C7B C8B C1B 104.5(4) . . ?
C7B C8B C9B 126.1(4) . . ?
C1B C8B C9B 117.4(4) . . ?
C7B C8B C10B 122.9(4) . . ?
C1B C8B C10B 122.6(4) . . ?
C9B C8B C10B 58.6(3) . . ?
C10B C9B C8B 61.1(3) . . ?
C9B C10B C11B 122.2(4) . . ?
C9B C10B C8B 60.3(3) . . ?
C11B C10B C8B 121.0(4) . . ?
C10B C11B C12B 114.5(4) . . ?
C13B C12B C17B 117.7(4) . . ?
C13B C12B C11B 120.4(4) . . ?
C17B C12B C11B 121.8(4) . . ?
C14B C13B C12B 121.6(5) . . ?
C13B C14B C15B 121.0(5) . . ?
C14B C15B C16B 117.3(4) . . ?
C14B C15B C18B 122.3(4) . . ?
C16B C15B C18B 120.4(4) . . ?
C17B C16B C15B 121.6(5) . . ?
C16B C17B C12B 120.8(5) . . ?
C19B C18B C23B 118.3(5) . . ?
C19B C18B C15B 120.8(5) . . ?
C23B C18B C15B 120.9(4) . . ?
C20B C19B C18B 121.0(5) . . ?
C21B C20B C19B 120.3(5) . . ?
C20B C21B C22B 119.4(5) . . ?
C21B C22B C23B 120.6(5) . . ?
C22B C23B C18B 120.3(5) . . ?

_refine_diff_density_max         0.896
_refine_diff_density_min         -0.654
_refine_diff_density_rms         0.160












_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
####################################################################### 
# 
# 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_mm103
_database_code_depnum_ccdc_archive 'CCDC 2307638'
loop_
_audit_author_name
_audit_author_address
'Giovanni Macetti'
;Universita degli Studi di Milano
Italy
;
_audit_update_record             
;
2023-11-13 deposited with the CCDC.	2024-02-14 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_THETM01_mm103               
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: The collected crystal exhibits a substantial presence of  disordered solvent molecules occupying the extensive void  volumes of the structure. This considerable intrinsic  disorder affects the overall quality of the crystal.  In particular, it reduces the intensity of all the  reflections, in particular those at high theta angles.  For this reasons, no data are observed above the indicated  value. We conducted tests on various samples, and the  collected one stands out the best available. Nevertheless,  considering that the primary objective of our study was to  determine the correct absolute configuration of the  molecule's stereocenters, the data quality proves to be  sufficiently accurate to achieve the purpose.
;
_vrf_RINTA01_mm103               
;
PROBLEM: The value of Rint is greater than 0.18
RESPONSE: The suboptimal data quality can be attributed to the coexistence of twinning crystals and disordered solvent molecules. We isolated the main twinned components, and also we employed the SQUEEZE procedure to mitigate the solvent's impact on the structure factors. Despite these measures, the internal agreement factor still exceeded 0.18.
;
_vrf_PLAT020_mm103               
;
PROBLEM: The Value of Rint is Greater Than 0.12 .........      0.213 Report
RESPONSE: The suboptimal data quality can be attributed to the  coexistence of twinning crystals and disordered solvent  molecules. We isolated the main twinned components, and also  we employed the SQUEEZE procedure to mitigate the solvent's  impact on the structure factors. Despite these measures,  the internal agreement factor is still equal to 0.213.
;
_vrf_PLAT026_mm103               
;
PROBLEM: Ratio Observed / Unique Reflections (too) Low ..        48% Check
RESPONSE: The structure factor intensities are significantly affected  by the low crystallinity of the sample. The issue arises due  to the substantial population of disordered solvent molecules  within the extensive voids, causing a substantial reduction  in the overall intensity of the collected data.
;
_vrf_PLAT029_mm103               
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.974 Why?
RESPONSE: The presence of twinning has inevitably resulted in a  reduction in the total number of collected data, potentially  leading to the exclusion of some unique reflection and  therefore yielding a fractional coverage less than 1.
;
_vrf_PLAT234_mm103               
;
PROBLEM: Large Hirshfeld Difference C4       --C5       .       0.16 Ang.
RESPONSE: These differences likely arise from the positioning of the pairs of atoms in the structure. The absence of strong intermolecular interactions, together with the suboptimal data quality, unavoidably results in an imperfect depiction of the peripheral atoms, specifically those more susceptible to libration and vibration movements.
;
_vrf_PLAT234_mm103_2             
;
PROBLEM: Large Hirshfeld Difference C7       --C8       .       0.16 Ang.
RESPONSE: These differences likely arise from the positioning of the pairs of atoms in the structure. The absence of strong intermolecular interactions, together with the suboptimal data quality, unavoidably results in an imperfect depiction of the peripheral atoms, specifically those more susceptible to libration and vibration movements.
;
_vrf_PLAT234_mm103_3             
;
PROBLEM: Large Hirshfeld Difference C11      --C12      .       0.17 Ang.
RESPONSE: These differences likely arise from the positioning of the pairs of atoms in the structure. The absence of strong intermolecular interactions, together with the suboptimal data quality, unavoidably results in an imperfect depiction of the peripheral atoms, specifically those more susceptible to libration and vibration movements.
;
_vrf_PLAT234_mm103_4             
;
PROBLEM: Large Hirshfeld Difference C19      --C20      .       0.23 Ang.
RESPONSE: These differences likely arise from the positioning of the pairs of atoms in the structure. The absence of strong intermolecular interactions, together with the suboptimal data quality, unavoidably results in an imperfect depiction of the peripheral atoms, specifically those more susceptible to libration and vibration movements.
;
_vrf_PLAT234_mm103_5             
;
PROBLEM: Large Hirshfeld Difference C20      --C21      .       0.24 Ang.
RESPONSE: These differences likely arise from the positioning of the pairs of atoms in the structure. The absence of strong intermolecular interactions, together with the suboptimal data quality, unavoidably results in an imperfect depiction of the peripheral atoms, specifically those more susceptible to libration and vibration movements.
;
_vrf_PLAT234_mm103_6             
;
PROBLEM: Large Hirshfeld Difference C38      --C39      .       0.17 Ang.
RESPONSE: These differences likely arise from the positioning of the pairs of atoms in the structure. The absence of strong intermolecular interactions, together with the suboptimal data quality, unavoidably results in an imperfect depiction of the peripheral atoms, specifically those more susceptible to libration and vibration movements.
;
_vrf_PLAT234_mm103_7             
;
PROBLEM: Large Hirshfeld Difference C40      --C45      .       0.16 Ang.
RESPONSE: These differences likely arise from the positioning of the pairs of atoms in the structure. The absence of strong intermolecular interactions, together with the suboptimal data quality, unavoidably results in an imperfect depiction of the peripheral atoms, specifically those more susceptible to libration and vibration movements.
;
_vrf_PLAT241_mm103               
;
PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of        C19 Check
RESPONSE: These atoms belong to the terminal benzene rings. Since the structure does not possess strong intermolecular interactions, the terminal atoms generally show larger ADPs than those close to the core.
;
_vrf_PLAT241_mm103_2             
;
PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of        C43 Check
RESPONSE: These atoms belong to the terminal benzene rings. Since the structure does not possess strong intermolecular interactions, the terminal atoms generally show larger ADPs than those close to the core.
;
_vrf_PLAT341_mm103               
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.01302 Ang.
RESPONSE: The bond precision is affected by the presence of both  twinning and disordered solvent molecules. Additionally, the  data collection was conducted at RT, a factor that further  impacts the overall precision. While conducting the experiment  at a low T could have improved the overall description of  the model, it is important to highlight that the main scope  of the study was to determine the absolute molecular  configuration. Therefore, we believe the obtained quality of  data is sufficiently high for the intended purpose.
;
_vrf_PLAT905_mm103               
;
PROBLEM: Negative K value in the Analysis of Variance ...     -5.624 Report
RESPONSE: Negative K value could be present considering that almost the  50% of the data have intensity lower than two times the standard  deviation. The reason of this is the presence of a twinned phase  and large intrinsic disorder of the solvent molecules.
;
_vrf_PLAT911_mm103               
;
PROBLEM: Missing FCF Refl Between Thmin & STh/L=    0.510        137 Report
RESPONSE: The absence of these reflections may be attributed to  the existence of twinning. Given our decision to exclusively  refine the major component, it is conceivable that certain  reflections were attributed to the minor twinned component.
;
_audit_creation_date             2023-10-20
_audit_creation_method           SHELXL-2018/3
_audit_conform_dict_name         cif_core.dic
_audit_conform_dict_version      2.4.5
_audit_conform_dict_location     ftp://ftp.iucr.org/pub/cif_core.dic

#------------------ CHEMICAL INFORMATION ------------------------------------#  
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          '525-527 K'
_chemical_formula_moiety         'C51 H28 Br N O2'
_chemical_formula_sum            'C51 H38 Br N O2'
_chemical_formula_weight         776.73

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 '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                   21.2019(13)
_cell_length_b                   9.5258(5)
_cell_length_c                   24.3433(12)
_cell_angle_alpha                90
_cell_angle_beta                 105.859(6)
_cell_angle_gamma                90
_cell_volume                     4729.3(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    4510
_cell_measurement_theta_min      3.2170
_cell_measurement_theta_max      50.0650

_exptl_crystal_description       needle
_exptl_crystal_colour            'translucent pale colorles'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.091
_exptl_crystal_F_000             1608
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          1.0
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_absorpt_coefficient_mu    1.454
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.64835
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_radiation_monochromator  mirror
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            HyPix
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       'ω scans'
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -55.00 -26.00   0.50   16.77    --   -0.55 -71.00 107.00   58
  2  ω    -21.00  11.00   0.50   16.77    --   -0.55  71.00-122.00   64
  3  ω     35.00 128.00   0.50   45.00    --   55.05  71.00-122.00  186
  4  ω     -5.00  75.00   0.50   45.00    --   55.05 -71.00 107.00  160
  5  ω   -114.00 -67.00   0.50   45.00    --  -56.15 -71.00 107.00   94
  6  ω    -70.00 -43.00   0.50   45.00    --  -56.15  71.00-122.00   54
  7  ω     75.00 101.00   0.50   45.00    --   55.05-125.00-180.00   52
  8  ω    -20.00   5.00   0.50   45.00    --   55.05 -19.00  90.00   50
  9  ω    -12.00  15.00   0.50   45.00    --   55.05 -19.00 150.00   54
 10  ω    -14.00  23.00   0.50   45.00    --   55.05 -19.00 -90.00   74
 11  ω    -20.00  24.00   0.50   45.00    --   55.05 -19.00 120.00   88
 12  ω   -126.00 -88.00   0.50   45.00    --  -56.15-125.00 -90.00   76
 13  ω    -39.00   7.00   0.50   45.00    --  -56.15  38.00-150.00   92
 14  ω    -24.00  16.00   0.50   45.00    --  -56.15  19.00  60.00   80
 15  ω    -44.00   8.00   0.50   45.00    --  -56.15  38.00   0.00  104
 16  ω   -126.00 -55.00   0.50   45.00    --  -56.15 -19.00   0.00  142
 17  ω    -66.00 -41.00   0.50   45.00    --  -56.15 -57.00  30.00   50
 18  ω   -127.00 -63.00   0.50   45.00    --  -56.15 -19.00 150.00  128
 19  ω   -102.00 -77.00   0.50   45.00    --  -56.15 -57.00  30.00   50
 20  ω   -124.00 -58.00   0.50   45.00    --  -56.15 -38.00 -30.00  132
 21  ω   -120.00 -73.00   0.50   45.00    --  -56.15-125.00-150.00   94
;
_diffrn_reflns_number            26125
_diffrn_reflns_av_unetI/netI     0.1430
_diffrn_reflns_av_R_equivalents  0.2132
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         3.239
_diffrn_reflns_theta_max         51.825
_diffrn_reflns_theta_full        51.825
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measured_fraction_theta_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_point_group_measured_fraction_full 0.974
_reflns_number_total             5126
_reflns_number_gt                2469
_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.
 
 Structure factors included contributions from the .fab file.
 
 _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 1.171.42.90a (Rigaku OD, 2023)'
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_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          
;The SQUEEZE correction was applied to remove the contribution of highly 
disordered CH2Cl2 molecules,SQUEEZE
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1013P)²] 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         5126
_refine_ls_number_parameters     496
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1506
_refine_ls_R_factor_gt           0.0732
_refine_ls_wR_factor_ref         0.2096
_refine_ls_wR_factor_gt          0.1707
_refine_ls_goodness_of_fit_ref   0.950
_refine_ls_restrained_S_all      0.950
_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 0.11233(6) 0.31909(11) 0.05260(4) 0.1088(5) Uani 1 1 d . . . . .
O1 O 0.0698(2) 0.7206(5) 0.2283(2) 0.0650(14) Uani 1 1 d . . . . .
O2 O 0.1626(3) 0.4628(6) 0.3940(2) 0.0730(17) Uani 1 1 d . . . . .
N1 N 0.1778(3) 0.6075(6) 0.4737(2) 0.0590(17) Uani 1 1 d . . . . .
C1 C 0.2141(4) 0.5937(7) 0.2967(3) 0.0527(19) Uani 1 1 d . . . . .
H1 H 0.229922 0.551403 0.335168 0.063 Uiso 1 1 calc R U . . .
C2 C 0.1463(4) 0.5308(8) 0.2673(3) 0.060(2) Uani 1 1 d . . . . .
H2 H 0.135654 0.446188 0.286609 0.072 Uiso 1 1 calc R U . . .
C3 C 0.1213(4) 0.5252(8) 0.2041(3) 0.062(2) Uani 1 1 d . . . . .
C4 C 0.1316(4) 0.4294(8) 0.1643(4) 0.069(2) Uani 1 1 d . . . . .
H4 H 0.159359 0.351640 0.175686 0.082 Uiso 1 1 calc R U . . .
C5 C 0.0998(5) 0.4520(10) 0.1080(4) 0.071(2) Uani 1 1 d . . . . .
C6 C 0.0584(4) 0.5662(11) 0.0893(3) 0.081(3) Uani 1 1 d . . . . .
H6 H 0.037811 0.578596 0.050222 0.098 Uiso 1 1 calc R U . . .
C7 C 0.0480(4) 0.6610(9) 0.1288(4) 0.079(3) Uani 1 1 d . . . . .
H7 H 0.020828 0.739664 0.117465 0.094 Uiso 1 1 calc R U . . .
C8 C 0.0787(4) 0.6362(9) 0.1852(3) 0.065(2) Uani 1 1 d . . . . .
C9 C 0.1129(4) 0.6682(7) 0.2814(3) 0.054(2) Uani 1 1 d . . . . .
C10 C 0.1815(4) 0.7375(7) 0.3027(3) 0.056(2) Uani 1 1 d . . . . .
H10 H 0.189622 0.810281 0.276401 0.067 Uiso 1 1 calc R U . . .
C11 C 0.2703(4) 0.5969(7) 0.2700(3) 0.054(2) Uani 1 1 d . . . . .
C12 C 0.3304(4) 0.5488(7) 0.3007(3) 0.061(2) Uani 1 1 d . . . . .
H12 H 0.334299 0.507114 0.336441 0.073 Uiso 1 1 calc R U . . .
C13 C 0.3860(4) 0.5590(7) 0.2809(3) 0.062(2) Uani 1 1 d . . . . .
H13 H 0.426682 0.527578 0.303984 0.075 Uiso 1 1 calc R U . . .
C14 C 0.3818(4) 0.6154(7) 0.2274(3) 0.054(2) Uani 1 1 d . . . . .
C15 C 0.3218(4) 0.6618(7) 0.1963(3) 0.061(2) Uani 1 1 d . . . . .
H15 H 0.317454 0.701172 0.160056 0.073 Uiso 1 1 calc R U . . .
C16 C 0.2663(4) 0.6522(7) 0.2170(3) 0.058(2) Uani 1 1 d . . . . .
H16 H 0.225660 0.684191 0.194184 0.069 Uiso 1 1 calc R U . . .
C17 C 0.4415(4) 0.6289(9) 0.2061(3) 0.062(2) Uani 1 1 d . . . . .
C18 C 0.4940(4) 0.5353(9) 0.2246(3) 0.077(3) Uani 1 1 d . . . . .
H18 H 0.491332 0.462656 0.250063 0.092 Uiso 1 1 calc R U . . .
C19 C 0.5510(5) 0.5491(12) 0.2053(4) 0.109(3) Uani 1 1 d . . . . .
H19 H 0.587628 0.490583 0.219031 0.131 Uiso 1 1 calc R U . . .
C20 C 0.5502(6) 0.6523(13) 0.1656(4) 0.105(4) Uani 1 1 d . . . . .
H20 H 0.585946 0.659587 0.149900 0.126 Uiso 1 1 calc R U . . .
C21 C 0.4993(6) 0.7446(11) 0.1481(4) 0.094(3) Uani 1 1 d . . . . .
H21 H 0.502134 0.817973 0.123097 0.113 Uiso 1 1 calc R U . . .
C22 C 0.4448(4) 0.7312(9) 0.1665(3) 0.079(3) Uani 1 1 d . . . . .
H22 H 0.408957 0.791615 0.152283 0.094 Uiso 1 1 calc R U . . .
C23 C 0.0798(4) 0.6802(8) 0.3296(3) 0.064(2) Uani 1 1 d . . . . .
H23A H 0.047043 0.755390 0.321304 0.077 Uiso 1 1 calc R U . . .
H23B H 0.057782 0.591928 0.333667 0.077 Uiso 1 1 calc R U . . .
C24 C 0.1322(4) 0.7123(7) 0.3837(3) 0.057(2) Uani 1 1 d . . . . .
C25 C 0.1872(4) 0.7924(7) 0.3625(3) 0.057(2) Uani 1 1 d . . . . .
H25A H 0.179833 0.893994 0.361760 0.068 Uiso 1 1 calc R U . . .
H25B H 0.230844 0.772481 0.387861 0.068 Uiso 1 1 calc R U . . .
C26 C 0.1455(4) 0.7344(8) 0.4825(3) 0.057(2) Uani 1 1 d . . . . .
C27 C 0.1407(4) 0.7955(9) 0.5333(3) 0.072(2) Uani 1 1 d . . . . .
H27 H 0.160155 0.753617 0.568851 0.086 Uiso 1 1 calc R U . . .
C28 C 0.1060(5) 0.9210(10) 0.5292(4) 0.082(3) Uani 1 1 d . . . . .
H28 H 0.102671 0.965885 0.562643 0.099 Uiso 1 1 calc R U . . .
C29 C 0.0768(4) 0.9801(8) 0.4773(4) 0.076(3) Uani 1 1 d . . . . .
H29 H 0.052123 1.062748 0.475601 0.092 Uiso 1 1 calc R U . . .
C30 C 0.0828(4) 0.9206(9) 0.4275(3) 0.067(2) Uani 1 1 d . . . . .
H30 H 0.064165 0.964391 0.392146 0.080 Uiso 1 1 calc R U . . .
C31 C 0.1163(4) 0.7964(9) 0.4301(3) 0.057(2) Uani 1 1 d . . . . .
C32 C 0.1601(4) 0.5768(9) 0.4168(3) 0.058(2) Uani 1 1 d . . . . .
C33 C 0.2072(4) 0.5089(8) 0.5210(3) 0.061(2) Uani 1 1 d . . . . .
C34 C 0.1508(4) 0.4596(8) 0.5463(4) 0.063(2) Uani 1 1 d . . . . .
C35 C 0.1547(5) 0.4763(9) 0.6036(4) 0.099(3) Uani 1 1 d . . . . .
H35 H 0.191512 0.518509 0.628767 0.119 Uiso 1 1 calc R U . . .
C36 C 0.1020(6) 0.4283(13) 0.6231(4) 0.122(4) Uani 1 1 d . . . . .
H36 H 0.103704 0.437988 0.661867 0.146 Uiso 1 1 calc R U . . .
C37 C 0.0483(6) 0.3675(11) 0.5865(6) 0.118(4) Uani 1 1 d . . . . .
H37 H 0.013779 0.334668 0.600416 0.141 Uiso 1 1 calc R U . . .
C38 C 0.0445(4) 0.3545(9) 0.5296(5) 0.092(3) Uani 1 1 d . . . . .
H38 H 0.007606 0.313576 0.504184 0.110 Uiso 1 1 calc R U . . .
C39 C 0.0964(5) 0.4028(9) 0.5104(4) 0.078(3) Uani 1 1 d . . . . .
H39 H 0.093816 0.395998 0.471351 0.094 Uiso 1 1 calc R U . . .
C40 C 0.2665(4) 0.5750(11) 0.5636(4) 0.073(2) Uani 1 1 d . . . . .
C41 C 0.3018(5) 0.5009(10) 0.6117(4) 0.093(3) Uani 1 1 d . . . . .
H41 H 0.287062 0.411237 0.618592 0.111 Uiso 1 1 calc R U . . .
C42 C 0.3554(7) 0.5524(16) 0.6483(4) 0.122(4) Uani 1 1 d . . . . .
H42 H 0.377107 0.499142 0.680395 0.147 Uiso 1 1 calc R U . . .
C43 C 0.3799(6) 0.6842(18) 0.6398(6) 0.134(5) Uani 1 1 d . . . . .
H43 H 0.417129 0.721378 0.666201 0.161 Uiso 1 1 calc R U . . .
C44 C 0.3486(6) 0.7571(12) 0.5924(5) 0.106(3) Uani 1 1 d . . . . .
H44 H 0.365139 0.844558 0.585039 0.128 Uiso 1 1 calc R U . . .
C45 C 0.2923(5) 0.7038(11) 0.5544(4) 0.080(3) Uani 1 1 d . . . . .
H45 H 0.271232 0.756332 0.521881 0.096 Uiso 1 1 calc R U . . .
C46 C 0.2938(6) 0.1627(13) 0.4538(5) 0.114(4) Uani 1 1 d . . . . .
H46 H 0.313066 0.088616 0.438666 0.136 Uiso 1 1 calc R U . . .
C47 C 0.2480(5) 0.1335(10) 0.4828(4) 0.111(3) Uani 1 1 d . . . . .
H47 H 0.235896 0.040408 0.487656 0.133 Uiso 1 1 calc R U . . .
C48 C 0.2197(4) 0.2456(11) 0.5049(3) 0.082(3) Uani 1 1 d . . . . .
H48 H 0.188790 0.228118 0.525359 0.098 Uiso 1 1 calc R U . . .
C49 C 0.2374(4) 0.3815(9) 0.4966(3) 0.068(2) Uani 1 1 d . . . . .
C50 C 0.2859(4) 0.4070(9) 0.4695(3) 0.081(3) Uani 1 1 d . . . . .
H50 H 0.301077 0.498705 0.466586 0.097 Uiso 1 1 calc R U . . .
C51 C 0.3114(5) 0.2953(13) 0.4470(4) 0.100(3) Uani 1 1 d . . . . .
H51 H 0.342006 0.312352 0.426186 0.120 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 C5 1.920(7) . ?
O1 C8 1.376(8) . ?
O1 C9 1.452(8) . ?
O2 C32 1.226(8) . ?
N1 C32 1.363(9) . ?
N1 C26 1.434(8) . ?
N1 C33 1.486(8) . ?
C1 C11 1.506(9) . ?
C1 C2 1.542(9) . ?
C1 C10 1.559(9) . ?
C1 H1 0.9900 . ?
C2 C3 1.484(9) . ?
C2 C9 1.569(9) . ?
C2 H2 0.9900 . ?
C3 C8 1.384(9) . ?
C3 C4 1.391(9) . ?
C4 C5 1.369(10) . ?
C4 H4 0.9400 . ?
C5 C6 1.394(11) . ?
C6 C7 1.380(10) . ?
C6 H6 0.9400 . ?
C7 C8 1.369(10) . ?
C7 H7 0.9400 . ?
C9 C23 1.528(8) . ?
C9 C10 1.551(9) . ?
C10 C25 1.521(8) . ?
C10 H10 0.9900 . ?
C11 C12 1.367(9) . ?
C11 C16 1.374(9) . ?
C12 C13 1.393(9) . ?
C12 H12 0.9400 . ?
C13 C14 1.388(9) . ?
C13 H13 0.9400 . ?
C14 C15 1.365(9) . ?
C14 C17 1.500(10) . ?
C15 C16 1.402(9) . ?
C15 H15 0.9400 . ?
C16 H16 0.9400 . ?
C17 C22 1.386(10) . ?
C17 C18 1.400(10) . ?
C18 C19 1.418(11) . ?
C18 H18 0.9400 . ?
C19 C20 1.376(12) . ?
C19 H19 0.9400 . ?
C20 C21 1.366(12) . ?
C20 H20 0.9400 . ?
C21 C22 1.355(11) . ?
C21 H21 0.9400 . ?
C22 H22 0.9400 . ?
C23 C24 1.504(9) . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C24 C31 1.497(9) . ?
C24 C32 1.551(10) . ?
C24 C25 1.592(9) . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C26 C31 1.387(9) . ?
C26 C27 1.396(9) . ?
C27 C28 1.393(10) . ?
C27 H27 0.9400 . ?
C28 C29 1.367(10) . ?
C28 H28 0.9400 . ?
C29 C30 1.375(9) . ?
C29 H29 0.9400 . ?
C30 C31 1.373(9) . ?
C30 H30 0.9400 . ?
C33 C40 1.530(10) . ?
C33 C49 1.564(10) . ?
C33 C34 1.559(10) . ?
C34 C39 1.354(10) . ?
C34 C35 1.384(10) . ?
C35 C36 1.403(12) . ?
C35 H35 0.9400 . ?
C36 C37 1.368(13) . ?
C36 H36 0.9400 . ?
C37 C38 1.371(12) . ?
C37 H37 0.9400 . ?
C38 C39 1.386(11) . ?
C38 H38 0.9400 . ?
C39 H39 0.9400 . ?
C40 C45 1.386(11) . ?
C40 C41 1.397(11) . ?
C41 C42 1.331(13) . ?
C41 H41 0.9400 . ?
C42 C43 1.396(14) . ?
C42 H42 0.9400 . ?
C43 C44 1.355(13) . ?
C43 H43 0.9400 . ?
C44 C45 1.391(12) . ?
C44 H44 0.9400 . ?
C45 H45 0.9400 . ?
C46 C51 1.341(12) . ?
C46 C47 1.375(13) . ?
C46 H46 0.9400 . ?
C47 C48 1.402(11) . ?
C47 H47 0.9400 . ?
C48 C49 1.378(10) . ?
C48 H48 0.9400 . ?
C49 C50 1.387(10) . ?
C50 C51 1.372(11) . ?
C50 H50 0.9400 . ?
C51 H51 0.9400 . ?

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
C8 O1 C9 107.0(5) . . ?
C32 N1 C26 108.8(6) . . ?
C32 N1 C33 126.4(6) . . ?
C26 N1 C33 122.2(6) . . ?
C11 C1 C2 123.7(6) . . ?
C11 C1 C10 116.5(6) . . ?
C2 C1 C10 90.2(5) . . ?
C11 C1 H1 108.3 . . ?
C2 C1 H1 108.3 . . ?
C10 C1 H1 108.3 . . ?
C3 C2 C1 121.3(6) . . ?
C3 C2 C9 101.6(6) . . ?
C1 C2 C9 89.6(5) . . ?
C3 C2 H2 113.6 . . ?
C1 C2 H2 113.6 . . ?
C9 C2 H2 113.6 . . ?
C8 C3 C4 118.8(7) . . ?
C8 C3 C2 109.4(7) . . ?
C4 C3 C2 131.7(8) . . ?
C5 C4 C3 117.8(8) . . ?
C5 C4 H4 121.1 . . ?
C3 C4 H4 121.1 . . ?
C4 C5 C6 122.8(7) . . ?
C4 C5 Br1 118.4(8) . . ?
C6 C5 Br1 118.8(7) . . ?
C7 C6 C5 119.3(7) . . ?
C7 C6 H6 120.3 . . ?
C5 C6 H6 120.3 . . ?
C8 C7 C6 117.6(8) . . ?
C8 C7 H7 121.2 . . ?
C6 C7 H7 121.2 . . ?
C7 C8 O1 122.5(8) . . ?
C7 C8 C3 123.6(8) . . ?
O1 C8 C3 114.0(7) . . ?
O1 C9 C23 110.3(6) . . ?
O1 C9 C10 117.1(5) . . ?
C23 C9 C10 107.3(5) . . ?
O1 C9 C2 107.7(5) . . ?
C23 C9 C2 124.0(6) . . ?
C10 C9 C2 89.5(6) . . ?
C25 C10 C9 106.8(5) . . ?
C25 C10 C1 118.0(6) . . ?
C9 C10 C1 89.7(5) . . ?
C25 C10 H10 113.3 . . ?
C9 C10 H10 113.3 . . ?
C1 C10 H10 113.3 . . ?
C12 C11 C16 116.8(7) . . ?
C12 C11 C1 119.1(6) . . ?
C16 C11 C1 124.1(8) . . ?
C11 C12 C13 122.5(7) . . ?
C11 C12 H12 118.7 . . ?
C13 C12 H12 118.7 . . ?
C14 C13 C12 120.5(8) . . ?
C14 C13 H13 119.8 . . ?
C12 C13 H13 119.8 . . ?
C15 C14 C13 117.2(7) . . ?
C15 C14 C17 121.8(7) . . ?
C13 C14 C17 120.9(8) . . ?
C14 C15 C16 121.7(7) . . ?
C14 C15 H15 119.2 . . ?
C16 C15 H15 119.2 . . ?
C11 C16 C15 121.3(7) . . ?
C11 C16 H16 119.4 . . ?
C15 C16 H16 119.4 . . ?
C22 C17 C18 119.1(7) . . ?
C22 C17 C14 120.6(8) . . ?
C18 C17 C14 120.3(8) . . ?
C17 C18 C19 120.5(8) . . ?
C17 C18 H18 119.7 . . ?
C19 C18 H18 119.7 . . ?
C20 C19 C18 116.8(9) . . ?
C20 C19 H19 121.6 . . ?
C18 C19 H19 121.6 . . ?
C21 C20 C19 122.4(9) . . ?
C21 C20 H20 118.8 . . ?
C19 C20 H20 118.8 . . ?
C22 C21 C20 120.6(9) . . ?
C22 C21 H21 119.7 . . ?
C20 C21 H21 119.7 . . ?
C21 C22 C17 120.3(9) . . ?
C21 C22 H22 119.8 . . ?
C17 C22 H22 119.8 . . ?
C24 C23 C9 107.7(6) . . ?
C24 C23 H23A 110.2 . . ?
C9 C23 H23A 110.2 . . ?
C24 C23 H23B 110.2 . . ?
C9 C23 H23B 110.2 . . ?
H23A C23 H23B 108.5 . . ?
C31 C24 C23 120.3(7) . . ?
C31 C24 C32 100.7(6) . . ?
C23 C24 C32 111.8(6) . . ?
C31 C24 C25 108.9(5) . . ?
C23 C24 C25 104.2(5) . . ?
C32 C24 C25 111.0(6) . . ?
C10 C25 C24 105.7(5) . . ?
C10 C25 H25A 110.6 . . ?
C24 C25 H25A 110.6 . . ?
C10 C25 H25B 110.6 . . ?
C24 C25 H25B 110.6 . . ?
H25A C25 H25B 108.7 . . ?
C31 C26 C27 121.0(7) . . ?
C31 C26 N1 109.5(6) . . ?
C27 C26 N1 129.6(7) . . ?
C26 C27 C28 117.3(7) . . ?
C26 C27 H27 121.3 . . ?
C28 C27 H27 121.3 . . ?
C29 C28 C27 121.1(8) . . ?
C29 C28 H28 119.4 . . ?
C27 C28 H28 119.4 . . ?
C28 C29 C30 121.2(8) . . ?
C28 C29 H29 119.4 . . ?
C30 C29 H29 119.4 . . ?
C29 C30 C31 119.0(7) . . ?
C29 C30 H30 120.5 . . ?
C31 C30 H30 120.5 . . ?
C26 C31 C30 120.3(7) . . ?
C26 C31 C24 109.2(7) . . ?
C30 C31 C24 130.3(7) . . ?
O2 C32 N1 128.0(7) . . ?
O2 C32 C24 124.0(7) . . ?
N1 C32 C24 108.0(7) . . ?
N1 C33 C40 110.9(6) . . ?
N1 C33 C49 108.9(6) . . ?
C40 C33 C49 103.3(7) . . ?
N1 C33 C34 107.0(6) . . ?
C40 C33 C34 115.7(7) . . ?
C49 C33 C34 110.8(6) . . ?
C39 C34 C35 120.2(8) . . ?
C39 C34 C33 118.3(7) . . ?
C35 C34 C33 121.5(8) . . ?
C34 C35 C36 117.9(9) . . ?
C34 C35 H35 121.0 . . ?
C36 C35 H35 121.0 . . ?
C37 C36 C35 121.1(10) . . ?
C37 C36 H36 119.4 . . ?
C35 C36 H36 119.4 . . ?
C38 C37 C36 120.2(9) . . ?
C38 C37 H37 119.9 . . ?
C36 C37 H37 119.9 . . ?
C37 C38 C39 118.6(10) . . ?
C37 C38 H38 120.7 . . ?
C39 C38 H38 120.7 . . ?
C34 C39 C38 121.9(9) . . ?
C34 C39 H39 119.0 . . ?
C38 C39 H39 119.0 . . ?
C45 C40 C41 116.0(9) . . ?
C45 C40 C33 122.9(9) . . ?
C41 C40 C33 120.8(9) . . ?
C42 C41 C40 122.6(10) . . ?
C42 C41 H41 118.7 . . ?
C40 C41 H41 118.7 . . ?
C41 C42 C43 121.1(12) . . ?
C41 C42 H42 119.4 . . ?
C43 C42 H42 119.4 . . ?
C44 C43 C42 118.1(11) . . ?
C44 C43 H43 120.9 . . ?
C42 C43 H43 120.9 . . ?
C43 C44 C45 120.7(11) . . ?
C43 C44 H44 119.6 . . ?
C45 C44 H44 119.6 . . ?
C40 C45 C44 121.4(9) . . ?
C40 C45 H45 119.3 . . ?
C44 C45 H45 119.3 . . ?
C51 C46 C47 120.9(9) . . ?
C51 C46 H46 119.6 . . ?
C47 C46 H46 119.6 . . ?
C46 C47 C48 118.6(9) . . ?
C46 C47 H47 120.7 . . ?
C48 C47 H47 120.7 . . ?
C49 C48 C47 119.8(8) . . ?
C49 C48 H48 120.1 . . ?
C47 C48 H48 120.1 . . ?
C48 C49 C50 120.1(8) . . ?
C48 C49 C33 121.1(7) . . ?
C50 C49 C33 118.7(8) . . ?
C51 C50 C49 118.5(9) . . ?
C51 C50 H50 120.7 . . ?
C49 C50 H50 120.7 . . ?
C46 C51 C50 121.9(9) . . ?
C46 C51 H51 119.1 . . ?
C50 C51 H51 119.1 . . ?

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 C1 C2 C3 -26.9(11) . . . . ?
C10 C1 C2 C3 95.7(7) . . . . ?
C11 C1 C2 C9 -130.3(7) . . . . ?
C10 C1 C2 C9 -7.8(5) . . . . ?
C1 C2 C3 C8 -99.0(8) . . . . ?
C9 C2 C3 C8 -2.2(8) . . . . ?
C1 C2 C3 C4 83.6(10) . . . . ?
C9 C2 C3 C4 -179.6(8) . . . . ?
C8 C3 C4 C5 1.4(11) . . . . ?
C2 C3 C4 C5 178.6(8) . . . . ?
C3 C4 C5 C6 0.3(12) . . . . ?
C3 C4 C5 Br1 -179.0(5) . . . . ?
C4 C5 C6 C7 -0.5(13) . . . . ?
Br1 C5 C6 C7 178.7(6) . . . . ?
C5 C6 C7 C8 -0.9(12) . . . . ?
C6 C7 C8 O1 -177.4(7) . . . . ?
C6 C7 C8 C3 2.7(12) . . . . ?
C9 O1 C8 C7 -176.3(7) . . . . ?
C9 O1 C8 C3 3.6(8) . . . . ?
C4 C3 C8 C7 -3.0(12) . . . . ?
C2 C3 C8 C7 179.2(7) . . . . ?
C4 C3 C8 O1 177.1(6) . . . . ?
C2 C3 C8 O1 -0.7(9) . . . . ?
C8 O1 C9 C23 -143.0(6) . . . . ?
C8 O1 C9 C10 94.0(7) . . . . ?
C8 O1 C9 C2 -4.8(7) . . . . ?
C3 C2 C9 O1 4.3(7) . . . . ?
C1 C2 C9 O1 126.2(5) . . . . ?
C3 C2 C9 C23 135.3(7) . . . . ?
C1 C2 C9 C23 -102.8(7) . . . . ?
C3 C2 C9 C10 -114.1(6) . . . . ?
C1 C2 C9 C10 7.8(5) . . . . ?
O1 C9 C10 C25 123.3(6) . . . . ?
C23 C9 C10 C25 -1.3(8) . . . . ?
C2 C9 C10 C25 -127.0(5) . . . . ?
O1 C9 C10 C1 -117.4(6) . . . . ?
C23 C9 C10 C1 118.0(6) . . . . ?
C2 C9 C10 C1 -7.7(5) . . . . ?
C11 C1 C10 C25 -114.8(7) . . . . ?
C2 C1 C10 C25 116.8(6) . . . . ?
C11 C1 C10 C9 136.3(7) . . . . ?
C2 C1 C10 C9 7.8(5) . . . . ?
C2 C1 C11 C12 -129.7(8) . . . . ?
C10 C1 C11 C12 120.5(7) . . . . ?
C2 C1 C11 C16 53.6(10) . . . . ?
C10 C1 C11 C16 -56.1(10) . . . . ?
C16 C11 C12 C13 2.4(11) . . . . ?
C1 C11 C12 C13 -174.5(6) . . . . ?
C11 C12 C13 C14 -2.3(11) . . . . ?
C12 C13 C14 C15 1.2(10) . . . . ?
C12 C13 C14 C17 179.1(6) . . . . ?
C13 C14 C15 C16 -0.5(10) . . . . ?
C17 C14 C15 C16 -178.4(6) . . . . ?
C12 C11 C16 C15 -1.6(10) . . . . ?
C1 C11 C16 C15 175.1(7) . . . . ?
C14 C15 C16 C11 0.8(11) . . . . ?
C15 C14 C17 C22 24.4(11) . . . . ?
C13 C14 C17 C22 -153.4(7) . . . . ?
C15 C14 C17 C18 -153.6(7) . . . . ?
C13 C14 C17 C18 28.7(10) . . . . ?
C22 C17 C18 C19 3.1(12) . . . . ?
C14 C17 C18 C19 -178.9(7) . . . . ?
C17 C18 C19 C20 -3.7(13) . . . . ?
C18 C19 C20 C21 4.6(15) . . . . ?
C19 C20 C21 C22 -4.9(16) . . . . ?
C20 C21 C22 C17 4.0(15) . . . . ?
C18 C17 C22 C21 -3.2(12) . . . . ?
C14 C17 C22 C21 178.8(8) . . . . ?
O1 C9 C23 C24 -145.7(6) . . . . ?
C10 C9 C23 C24 -17.1(8) . . . . ?
C2 C9 C23 C24 84.3(9) . . . . ?
C9 C23 C24 C31 150.1(6) . . . . ?
C9 C23 C24 C32 -92.2(7) . . . . ?
C9 C23 C24 C25 27.7(7) . . . . ?
C9 C10 C25 C24 18.0(7) . . . . ?
C1 C10 C25 C24 -80.8(7) . . . . ?
C31 C24 C25 C10 -157.9(6) . . . . ?
C23 C24 C25 C10 -28.3(7) . . . . ?
C32 C24 C25 C10 92.2(7) . . . . ?
C32 N1 C26 C31 -10.1(8) . . . . ?
C33 N1 C26 C31 -172.9(6) . . . . ?
C32 N1 C26 C27 169.6(7) . . . . ?
C33 N1 C26 C27 6.9(11) . . . . ?
C31 C26 C27 C28 -0.5(11) . . . . ?
N1 C26 C27 C28 179.8(7) . . . . ?
C26 C27 C28 C29 1.3(12) . . . . ?
C27 C28 C29 C30 -2.6(13) . . . . ?
C28 C29 C30 C31 3.0(12) . . . . ?
C27 C26 C31 C30 0.9(11) . . . . ?
N1 C26 C31 C30 -179.3(6) . . . . ?
C27 C26 C31 C24 177.2(6) . . . . ?
N1 C26 C31 C24 -3.1(8) . . . . ?
C29 C30 C31 C26 -2.1(11) . . . . ?
C29 C30 C31 C24 -177.5(7) . . . . ?
C23 C24 C31 C26 136.3(7) . . . . ?
C32 C24 C31 C26 13.0(8) . . . . ?
C25 C24 C31 C26 -103.7(7) . . . . ?
C23 C24 C31 C30 -48.0(11) . . . . ?
C32 C24 C31 C30 -171.2(8) . . . . ?
C25 C24 C31 C30 72.1(10) . . . . ?
C26 N1 C32 O2 -158.9(7) . . . . ?
C33 N1 C32 O2 2.9(12) . . . . ?
C26 N1 C32 C24 18.5(7) . . . . ?
C33 N1 C32 C24 -179.6(6) . . . . ?
C31 C24 C32 O2 158.4(7) . . . . ?
C23 C24 C32 O2 29.4(9) . . . . ?
C25 C24 C32 O2 -86.4(8) . . . . ?
C31 C24 C32 N1 -19.2(7) . . . . ?
C23 C24 C32 N1 -148.1(6) . . . . ?
C25 C24 C32 N1 96.0(6) . . . . ?
C32 N1 C33 C40 132.8(7) . . . . ?
C26 N1 C33 C40 -67.6(8) . . . . ?
C32 N1 C33 C49 19.7(10) . . . . ?
C26 N1 C33 C49 179.3(6) . . . . ?
C32 N1 C33 C34 -100.1(8) . . . . ?
C26 N1 C33 C34 59.5(8) . . . . ?
N1 C33 C34 C39 54.5(9) . . . . ?
C40 C33 C34 C39 178.7(7) . . . . ?
C49 C33 C34 C39 -64.1(9) . . . . ?
N1 C33 C34 C35 -123.8(8) . . . . ?
C40 C33 C34 C35 0.4(11) . . . . ?
C49 C33 C34 C35 117.6(8) . . . . ?
C39 C34 C35 C36 2.2(13) . . . . ?
C33 C34 C35 C36 -179.6(8) . . . . ?
C34 C35 C36 C37 -0.4(16) . . . . ?
C35 C36 C37 C38 -1.0(18) . . . . ?
C36 C37 C38 C39 0.5(16) . . . . ?
C35 C34 C39 C38 -2.7(13) . . . . ?
C33 C34 C39 C38 179.0(7) . . . . ?
C37 C38 C39 C34 1.3(13) . . . . ?
N1 C33 C40 C45 -6.5(10) . . . . ?
C49 C33 C40 C45 110.1(8) . . . . ?
C34 C33 C40 C45 -128.7(8) . . . . ?
N1 C33 C40 C41 179.9(7) . . . . ?
C49 C33 C40 C41 -63.6(9) . . . . ?
C34 C33 C40 C41 57.7(10) . . . . ?
C45 C40 C41 C42 2.8(13) . . . . ?
C33 C40 C41 C42 176.9(9) . . . . ?
C40 C41 C42 C43 -0.9(17) . . . . ?
C41 C42 C43 C44 -1.7(18) . . . . ?
C42 C43 C44 C45 2.2(17) . . . . ?
C41 C40 C45 C44 -2.2(12) . . . . ?
C33 C40 C45 C44 -176.1(8) . . . . ?
C43 C44 C45 C40 -0.3(15) . . . . ?
C51 C46 C47 C48 0.2(17) . . . . ?
C46 C47 C48 C49 1.0(15) . . . . ?
C47 C48 C49 C50 -4.0(13) . . . . ?
C47 C48 C49 C33 -179.6(8) . . . . ?
N1 C33 C49 C48 -125.3(8) . . . . ?
C40 C33 C49 C48 116.7(8) . . . . ?
C34 C33 C49 C48 -7.8(11) . . . . ?
N1 C33 C49 C50 59.0(10) . . . . ?
C40 C33 C49 C50 -58.9(9) . . . . ?
C34 C33 C49 C50 176.5(8) . . . . ?
C48 C49 C50 C51 5.7(13) . . . . ?
C33 C49 C50 C51 -178.6(7) . . . . ?
C47 C46 C51 C50 1.6(17) . . . . ?
C49 C50 C51 C46 -4.5(15) . . . . ?

_refine_diff_density_max         0.324
_refine_diff_density_min         -0.413
_refine_diff_density_rms         0.059







_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: DCM'
