# Supplementary Information (SI) for CrystEngComm.
# 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. 
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data_tpa_hdme_acti
_database_code_depnum_ccdc_archive 'CCDC 2344711'
loop_
_audit_author_name
_audit_author_address
'Mark D. Smith'
;University of South Carolina
United States of America
;
_audit_update_record             
;
2024-03-31 deposited with the CCDC.	2024-10-02 downloaded from the CCDC.
;
_audit_creation_date             2023-06-20
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_shelx_SHELXL_version_number     2019/2
# end Validation Reply Form
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C42 H38 N6 O2'
_chemical_formula_sum            'C42 H38 N6 O2'
_chemical_formula_weight         658.78
_chemical_melting_point          ?
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'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.845(3)
_cell_length_b                   4.6481(9)
_cell_length_c                   26.022(5)
_cell_angle_alpha                90
_cell_angle_beta                 104.992(5)
_cell_angle_gamma                90
_cell_volume                     1851.3(6)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    2404
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.278
_cell_measurement_theta_min      2.348
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.074
_exptl_absorpt_correction_T_max  0.6181
_exptl_absorpt_correction_T_min  0.4358
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1348 before and 0.0704 after correction.
The Ratio of minimum to maximum transmission is 0.7051.
The λ/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.182
_exptl_crystal_description       needle
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_diffrn_reflns_av_R_equivalents  0.0975
_diffrn_reflns_av_unetI/netI     0.0766
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_k_min       -4
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            9991
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        21.327
_diffrn_reflns_theta_max         21.327
_diffrn_reflns_theta_min         2.661
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 PHOTON-II
_diffrn_detector_area_resol_mean 7.39
_diffrn_detector_type            'area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          X-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_special_details          ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1648
_reflns_number_total             2069
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'Bruker APEX3 v2019.1-0 (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_refine_diff_density_max         0.910
_refine_diff_density_min         -0.229
_refine_diff_density_rms         0.067
_refine_ls_extinction_coef       0.0073(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.222
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     234
_refine_ls_number_reflns         2069
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.1440
_refine_ls_R_factor_gt           0.1165
_refine_ls_restrained_S_all      1.222
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0412P)²+9.6101P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2137
_refine_ls_wR_factor_ref         0.2254
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 N1-H1 \\sim N2-H2
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(H1) = Uiso(H2)
4.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C21(H21A,H21B)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C16(H16), C17(H17), C19(H19), C20(H20)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
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
O1 O 0.5839(3) 0.0683(11) 0.33284(19) 0.0304(14) Uani 1 1 d . . . . .
N1 N 0.6572(4) 0.4944(14) 0.3468(2) 0.0254(15) Uani 1 1 d D . . . .
N2 N 0.5092(4) 0.4876(14) 0.3149(2) 0.0284(16) Uani 1 1 d D . . . .
N3 N 0.1630(4) 0.6521(14) 0.4012(2) 0.0336(17) Uani 1 1 d . . . . .
C1 C 0.5836(4) 0.3323(17) 0.3318(2) 0.0194(17) Uani 1 1 d . . . . .
C2 C 0.4241(4) 0.3585(18) 0.2921(3) 0.037(2) Uani 1 1 d . . . . .
H2A H 0.430593 0.146550 0.292766 0.044 Uiso 1 1 calc R U . . .
H2B H 0.403562 0.418260 0.254364 0.044 Uiso 1 1 calc R U . . .
C3 C 0.3555(4) 0.4399(17) 0.3207(3) 0.029(2) Uani 1 1 d . . . . .
C4 C 0.2925(4) 0.6434(17) 0.3011(3) 0.033(2) Uani 1 1 d . . . . .
H4 H 0.291851 0.735903 0.268498 0.040 Uiso 1 1 calc R U . . .
C5 C 0.2303(5) 0.7180(19) 0.3271(3) 0.036(2) Uani 1 1 d . . . . .
H5 H 0.188248 0.861410 0.312443 0.043 Uiso 1 1 calc R U . . .
C6 C 0.2287(4) 0.5857(16) 0.3743(3) 0.027(2) Uani 1 1 d . . . . .
C7 C 0.2920(5) 0.3825(18) 0.3952(3) 0.044(2) Uani 1 1 d . . . . .
H7 H 0.291892 0.289335 0.427683 0.053 Uiso 1 1 calc R U . . .
C8 C 0.3560(5) 0.3123(18) 0.3691(3) 0.044(2) Uani 1 1 d . . . . .
H8 H 0.400118 0.176701 0.384585 0.053 Uiso 1 1 calc R U . . .
C9 C 0.0761(4) 0.6995(17) 0.3715(3) 0.0262(19) Uani 1 1 d . . . . .
C10 C 0.0405(5) 0.553(2) 0.3250(3) 0.045(2) Uani 1 1 d . . . . .
H10 H 0.074166 0.412285 0.312616 0.054 Uiso 1 1 calc R U . . .
C11 C -0.0441(5) 0.610(2) 0.2963(3) 0.057(3) Uani 1 1 d . . . . .
H11 H -0.066945 0.508672 0.263971 0.069 Uiso 1 1 calc R U . . .
C12 C -0.0964(5) 0.804(2) 0.3124(4) 0.058(3) Uani 1 1 d . . . . .
H12 H -0.154537 0.841263 0.292283 0.070 Uiso 1 1 calc R U . . .
C13 C -0.0602(6) 0.942(2) 0.3592(4) 0.070(3) Uani 1 1 d . . . . .
H13 H -0.095006 1.077084 0.372036 0.084 Uiso 1 1 calc R U . . .
C14 C 0.0243(5) 0.8959(19) 0.3888(3) 0.054(3) Uani 1 1 d . . . . .
H14 H 0.046841 0.999020 0.420934 0.065 Uiso 1 1 calc R U . . .
C15 C 0.1858(4) 0.6498(16) 0.4584(3) 0.030(2) Uani 1 1 d . . . . .
C16 C 0.1308(5) 0.5333(18) 0.4865(3) 0.034(2) Uani 1 1 d . . . . .
H16 H 0.076455 0.453097 0.467621 0.041 Uiso 1 1 calc R U . . .
C17 C 0.1531(4) 0.5314(18) 0.5410(3) 0.032(2) Uani 1 1 d . . . . .
H17 H 0.113430 0.451879 0.559016 0.038 Uiso 1 1 calc R U . . .
C18 C 0.2321(4) 0.6427(15) 0.5707(3) 0.0217(18) Uani 1 1 d . . . . .
C19 C 0.2871(4) 0.7617(17) 0.5420(3) 0.033(2) Uani 1 1 d . . . . .
H19 H 0.341470 0.841812 0.560805 0.039 Uiso 1 1 calc R U . . .
C20 C 0.2643(5) 0.7656(17) 0.4874(3) 0.034(2) Uani 1 1 d . . . . .
H20 H 0.303045 0.849158 0.469154 0.041 Uiso 1 1 calc R U . . .
C21 C 0.2580(4) 0.6366(17) 0.6306(3) 0.030(2) Uani 1 1 d . . . . .
H21A H 0.258874 0.836186 0.643990 0.036 Uiso 1 1 calc R U . . .
H21B H 0.213117 0.529013 0.643041 0.036 Uiso 1 1 calc R U . . .
H2 H 0.515(5) 0.681(13) 0.315(3) 0.039(17) Uiso 1 1 d D . . . .
H1 H 0.656(5) 0.688(13) 0.344(3) 0.039(17) Uiso 1 1 d 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
O1 C1 1.228(8) . ?
N1 C1 1.359(9) . ?
N1 C21 1.453(9) 3_666 ?
N1 H1 0.90(6) . ?
N2 C1 1.354(9) . ?
N2 C2 1.455(9) . ?
N2 H2 0.91(6) . ?
N3 C6 1.430(9) . ?
N3 C9 1.411(8) . ?
N3 C15 1.437(9) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C2 C3 1.517(10) . ?
C3 C4 1.374(10) . ?
C3 C8 1.391(10) . ?
C4 H4 0.9500 . ?
C4 C5 1.375(10) . ?
C5 H5 0.9500 . ?
C5 C6 1.381(10) . ?
C6 C7 1.382(10) . ?
C7 H7 0.9500 . ?
C7 C8 1.397(11) . ?
C8 H8 0.9500 . ?
C9 C10 1.377(10) . ?
C9 C14 1.378(11) . ?
C10 H10 0.9500 . ?
C10 C11 1.381(11) . ?
C11 H11 0.9500 . ?
C11 C12 1.363(13) . ?
C12 H12 0.9500 . ?
C12 C13 1.365(13) . ?
C13 H13 0.9500 . ?
C13 C14 1.379(11) . ?
C14 H14 0.9500 . ?
C15 C16 1.385(10) . ?
C15 C20 1.387(10) . ?
C16 H16 0.9500 . ?
C16 C17 1.370(10) . ?
C17 H17 0.9500 . ?
C17 C18 1.390(9) . ?
C18 C19 1.398(10) . ?
C18 C21 1.507(9) . ?
C19 H19 0.9500 . ?
C19 C20 1.374(10) . ?
C20 H20 0.9500 . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?

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
C1 N1 C21 121.3(6) . 3_666 ?
C1 N1 H1 122(5) . . ?
C21 N1 H1 117(5) 3_666 . ?
C1 N2 C2 123.3(6) . . ?
C1 N2 H2 117(5) . . ?
C2 N2 H2 120(5) . . ?
C6 N3 C15 119.0(5) . . ?
C9 N3 C6 119.8(6) . . ?
C9 N3 C15 121.1(6) . . ?
O1 C1 N1 123.3(6) . . ?
O1 C1 N2 122.6(7) . . ?
N2 C1 N1 114.1(7) . . ?
N2 C2 H2A 108.8 . . ?
N2 C2 H2B 108.8 . . ?
N2 C2 C3 113.7(6) . . ?
H2A C2 H2B 107.7 . . ?
C3 C2 H2A 108.8 . . ?
C3 C2 H2B 108.8 . . ?
C4 C3 C2 122.3(7) . . ?
C4 C3 C8 117.5(7) . . ?
C8 C3 C2 120.1(7) . . ?
C3 C4 H4 118.8 . . ?
C3 C4 C5 122.4(7) . . ?
C5 C4 H4 118.8 . . ?
C4 C5 H5 119.8 . . ?
C4 C5 C6 120.3(7) . . ?
C6 C5 H5 119.8 . . ?
C5 C6 N3 121.5(6) . . ?
C5 C6 C7 118.4(7) . . ?
C7 C6 N3 120.1(7) . . ?
C6 C7 H7 119.6 . . ?
C6 C7 C8 120.8(7) . . ?
C8 C7 H7 119.6 . . ?
C3 C8 C7 120.4(7) . . ?
C3 C8 H8 119.8 . . ?
C7 C8 H8 119.8 . . ?
C10 C9 N3 121.6(7) . . ?
C10 C9 C14 118.2(7) . . ?
C14 C9 N3 120.3(7) . . ?
C9 C10 H10 120.0 . . ?
C9 C10 C11 120.0(9) . . ?
C11 C10 H10 120.0 . . ?
C10 C11 H11 118.5 . . ?
C12 C11 C10 122.9(9) . . ?
C12 C11 H11 118.5 . . ?
C11 C12 H12 122.0 . . ?
C11 C12 C13 115.9(8) . . ?
C13 C12 H12 122.0 . . ?
C12 C13 H13 118.4 . . ?
C12 C13 C14 123.2(9) . . ?
C14 C13 H13 118.4 . . ?
C9 C14 C13 119.8(8) . . ?
C9 C14 H14 120.1 . . ?
C13 C14 H14 120.1 . . ?
C16 C15 N3 121.7(6) . . ?
C16 C15 C20 117.6(7) . . ?
C20 C15 N3 120.7(7) . . ?
C15 C16 H16 119.3 . . ?
C17 C16 C15 121.4(7) . . ?
C17 C16 H16 119.3 . . ?
C16 C17 H17 119.1 . . ?
C16 C17 C18 121.7(7) . . ?
C18 C17 H17 119.1 . . ?
C17 C18 C19 116.6(6) . . ?
C17 C18 C21 122.1(6) . . ?
C19 C18 C21 121.3(6) . . ?
C18 C19 H19 119.2 . . ?
C20 C19 C18 121.6(7) . . ?
C20 C19 H19 119.2 . . ?
C15 C20 H20 119.4 . . ?
C19 C20 C15 121.1(7) . . ?
C19 C20 H20 119.4 . . ?
N1 C21 C18 113.7(6) 3_666 . ?
N1 C21 H21A 108.8 3_666 . ?
N1 C21 H21B 108.8 3_666 . ?
C18 C21 H21A 108.8 . . ?
C18 C21 H21B 108.8 . . ?
H21A C21 H21B 107.7 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N2 H2 O1 0.91(6) 2.09(6) 2.935(8) 154(6) 1_565 yes
N1 H1 O1 0.90(6) 2.08(6) 2.895(8) 149(6) 1_565 yes

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
N2 C2 C3 C4 101.9(8) . . . . ?
N2 C2 C3 C8 -76.5(9) . . . . ?
N3 C6 C7 C8 179.2(7) . . . . ?
N3 C9 C10 C11 -178.5(8) . . . . ?
N3 C9 C14 C13 179.4(8) . . . . ?
N3 C15 C16 C17 179.9(7) . . . . ?
N3 C15 C20 C19 -179.3(7) . . . . ?
C1 N2 C2 C3 123.9(8) . . . . ?
C2 N2 C1 O1 -5.8(11) . . . . ?
C2 N2 C1 N1 173.6(6) . . . . ?
C2 C3 C4 C5 -179.8(7) . . . . ?
C2 C3 C8 C7 -178.8(7) . . . . ?
C3 C4 C5 C6 -0.7(12) . . . . ?
C4 C3 C8 C7 2.7(12) . . . . ?
C4 C5 C6 N3 -177.8(7) . . . . ?
C4 C5 C6 C7 1.4(11) . . . . ?
C5 C6 C7 C8 0.0(12) . . . . ?
C6 N3 C9 C10 34.1(11) . . . . ?
C6 N3 C9 C14 -146.1(8) . . . . ?
C6 N3 C15 C16 -138.4(7) . . . . ?
C6 N3 C15 C20 41.7(11) . . . . ?
C6 C7 C8 C3 -2.0(13) . . . . ?
C8 C3 C4 C5 -1.3(11) . . . . ?
C9 N3 C6 C5 38.8(10) . . . . ?
C9 N3 C6 C7 -140.4(7) . . . . ?
C9 N3 C15 C16 37.3(11) . . . . ?
C9 N3 C15 C20 -142.6(8) . . . . ?
C9 C10 C11 C12 -1.3(14) . . . . ?
C10 C9 C14 C13 -0.7(13) . . . . ?
C10 C11 C12 C13 -0.1(14) . . . . ?
C11 C12 C13 C14 1.1(15) . . . . ?
C12 C13 C14 C9 -0.7(15) . . . . ?
C14 C9 C10 C11 1.7(12) . . . . ?
C15 N3 C6 C5 -145.4(7) . . . . ?
C15 N3 C6 C7 35.4(10) . . . . ?
C15 N3 C9 C10 -141.6(8) . . . . ?
C15 N3 C9 C14 38.2(11) . . . . ?
C15 C16 C17 C18 -0.8(13) . . . . ?
C16 C15 C20 C19 0.8(12) . . . . ?
C16 C17 C18 C19 1.2(11) . . . . ?
C16 C17 C18 C21 -178.8(7) . . . . ?
C17 C18 C19 C20 -0.6(11) . . . . ?
C17 C18 C21 N1 126.5(7) . . . 3_666 ?
C18 C19 C20 C15 -0.3(12) . . . . ?
C19 C18 C21 N1 -53.6(10) . . . 3_666 ?
C20 C15 C16 C17 -0.2(12) . . . . ?
C21 N1 C1 O1 -4.9(11) 3_666 . . . ?
C21 N1 C1 N2 175.6(6) 3_666 . . . ?
C21 C18 C19 C20 179.4(7) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_vrf_PLAT097_tpa_hdme_acti       
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       0.91 eA-3  
RESPONSE: This peak is located 1.48 A from a phenyl carbon, and 2.75 A 
from a phenyl ring carbon from an adjacent molecule, i.e., in a sterically
implausible location. The peak refines to ca. 27% of a carbon atom. An
impurity (methyl, F) is inconsistent with synthetic procedure. It is likely
an artefact of unknown origin resulting from the moderate crystal quality.
;
_vrf_PLAT340_tpa_hdme_acti       
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0111 Ang.  
RESPONSE: Weakly diffracting light-atom needle crystals. Despite very slow
data collection rate per frame, intensities were weak and data quality is
only moderate.
;
# start Validation Reply Form
_vrf_THETM01_tpa_hdme_acti       
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE: Available crystals were weakly diffracting small needle
crystals containing no heavy atoms. The dataset was truncated at
sine(theta_max)/wavelength = 0.51, above which value no diffraction
ingtensity was observed.
;
####################################################################### 
# 
# 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_tpah_dme
_database_code_depnum_ccdc_archive 'CCDC 2344712'
loop_
_audit_author_name
_audit_author_address
'Mark D. Smith'
;University of South Carolina
United States of America
;
_audit_update_record             
;
2024-03-31 deposited with the CCDC.	2024-10-02 downloaded from the CCDC.
;
_audit_creation_date             2023-05-04
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_shelx_SHELXL_version_number     2018/3
# end Validation Reply Form
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C42 H38 N6 O2, 0.451(C4 H10 O2)'
_chemical_formula_sum            'C43.81 H42.51 N6 O2.90'
_chemical_formula_weight         699.40
_chemical_melting_point          ?
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'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.7922(12)
_cell_length_b                   4.7118(4)
_cell_length_c                   26.096(2)
_cell_angle_alpha                90
_cell_angle_beta                 104.800(2)
_cell_angle_gamma                90
_cell_volume                     1877.4(3)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    3214
_cell_measurement_temperature    301(2)
_cell_measurement_theta_max      24.724
_cell_measurement_theta_min      2.342
_shelx_estimated_absorpt_T_max   0.998
_shelx_estimated_absorpt_T_min   0.991
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  0.4899
_exptl_absorpt_correction_T_min  0.4501
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0971 before and 0.0607 after correction.
The Ratio of minimum to maximum transmission is 0.9188.
The λ/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       needle
_exptl_crystal_F_000             741
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.03
_diffrn_reflns_av_R_equivalents  0.0900
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            22436
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        23.256
_diffrn_reflns_theta_max         23.256
_diffrn_reflns_theta_min         2.342
_diffrn_ambient_temperature      301(2)
_diffrn_detector                 PHOTON-II
_diffrn_detector_area_resol_mean 7.39
_diffrn_detector_type            'area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          X-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1750
_reflns_number_total             2697
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'Bruker APEX3 v2019.1-0 (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_refine_diff_density_max         0.705
_refine_diff_density_min         -0.249
_refine_diff_density_rms         0.055
_refine_ls_extinction_coef       0.029(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         2697
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.1235
_refine_ls_R_factor_gt           0.0834
_refine_ls_restrained_S_all      1.057
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1086P)²+1.4389P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2040
_refine_ls_wR_factor_ref         0.2310
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O2S-C4S = O2S-C3S = O1S-C2S = O1S-C1S
 1.45 with sigma of 0.015
 C3S-C2S
 1.54 with sigma of 0.015
 O2S-C2S = O1S-C3S = C4S-C3S = C2S-C1S
 2.36 with sigma of 0.02
 H7-H1SB
 -2 with sigma of 0.02
3. Restrained planarity
 O1S, O2S, C1S, C2S, C3S, C4S
 with sigma of 0.1
4. Others
 Sof(O1S)=Sof(O2S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(H2SA)=
 Sof(H2SB)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(H4SC)=
 FVAR(1)
 Uiso(O1S)=Uiso(O2S)=Uiso(C1S)=Uiso(C2S)=Uiso(C3S)=Uiso(C4S)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C21(H21A,H21B), C2S(H2SA,H2SB), C3S(H3SA,H3SB)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C16(H16), C17(H17), C19(H19), C20(H20)
5.c Idealised Me refined with riding coordinates:
 C1S(H1SA,H1SB,H1SC)
5.d Idealised Me refined as rotating group:
 C4S(H4SA,H4SB,H4SC)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
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
O1 O 0.58121(19) 0.9029(6) 0.33454(12) 0.0674(9) Uani 1 1 d . . . . .
N1 N 0.5071(2) 0.4879(9) 0.31647(15) 0.0627(10) Uani 1 1 d . . . . .
H1 H 0.510(3) 0.294(11) 0.3145(16) 0.068(14) Uiso 1 1 d . . . . .
N2 N 0.6540(2) 0.4856(9) 0.35178(14) 0.0566(10) Uani 1 1 d . . . . .
H2 H 0.649(3) 0.303(10) 0.3548(16) 0.061(13) Uiso 1 1 d . . . . .
N3 N 0.8404(2) 0.6485(9) 0.60002(14) 0.0728(12) Uani 1 1 d . . . . .
C1 C 0.5810(3) 0.6412(9) 0.33432(14) 0.0490(10) Uani 1 1 d . . . . .
C2 C 0.7393(3) 0.6143(10) 0.37291(16) 0.0630(12) Uani 1 1 d . . . . .
H2A H 0.738267 0.805681 0.359052 0.076 Uiso 1 1 calc R U . . .
H2B H 0.782618 0.507641 0.360373 0.076 Uiso 1 1 calc R U . . .
C3 C 0.7675(3) 0.6269(9) 0.43237(16) 0.0539(11) Uani 1 1 d . . . . .
C4 C 0.8455(3) 0.5145(12) 0.46136(18) 0.0746(14) Uani 1 1 d . . . . .
H4 H 0.882853 0.430151 0.443437 0.090 Uiso 1 1 calc R U . . .
C5 C 0.8703(3) 0.5221(11) 0.51580(18) 0.0747(15) Uani 1 1 d . . . . .
H5 H 0.923475 0.442647 0.533842 0.090 Uiso 1 1 calc R U . . .
C6 C 0.8178(3) 0.6450(10) 0.54362(16) 0.0608(12) Uani 1 1 d . . . . .
C7 C 0.7399(3) 0.7623(11) 0.51573(18) 0.0742(14) Uani 1 1 d . . . . .
H7 H 0.703454 0.849688 0.533915 0.089 Uiso 1 1 calc DR U . . .
C8 C 0.7151(3) 0.7518(11) 0.46118(18) 0.0743(14) Uani 1 1 d . . . . .
H8 H 0.661838 0.830761 0.443253 0.089 Uiso 1 1 calc R U . . .
C9 C 0.9280(3) 0.7012(10) 0.62869(17) 0.0623(12) Uani 1 1 d . . . . .
C10 C 0.9779(4) 0.8953(12) 0.6107(3) 0.0997(19) Uani 1 1 d . . . . .
H10 H 0.954448 0.991353 0.579174 0.120 Uiso 1 1 calc R U . . .
C11 C 1.0621(4) 0.9495(16) 0.6389(4) 0.126(3) Uani 1 1 d . . . . .
H11 H 1.095337 1.081800 0.626131 0.151 Uiso 1 1 calc R U . . .
C12 C 1.0976(4) 0.813(2) 0.6851(4) 0.120(3) Uani 1 1 d . . . . .
H12 H 1.154753 0.850441 0.704155 0.144 Uiso 1 1 calc R U . . .
C13 C 1.0486(4) 0.6208(19) 0.7030(2) 0.117(3) Uani 1 1 d . . . . .
H13 H 1.072476 0.527196 0.734761 0.140 Uiso 1 1 calc R U . . .
C14 C 0.9642(3) 0.5606(14) 0.6752(2) 0.0907(17) Uani 1 1 d . . . . .
H14 H 0.931793 0.425204 0.687879 0.109 Uiso 1 1 calc R U . . .
C15 C 0.7757(3) 0.5865(10) 0.62724(16) 0.0591(11) Uani 1 1 d . . . . .
C16 C 0.7725(3) 0.7253(11) 0.67318(18) 0.0732(14) Uani 1 1 d . . . . .
H16 H 0.813352 0.866099 0.686711 0.088 Uiso 1 1 calc R U . . .
C17 C 0.7094(3) 0.6584(11) 0.69943(17) 0.0688(13) Uani 1 1 d . . . . .
H17 H 0.710197 0.751117 0.731006 0.083 Uiso 1 1 calc R U . . .
C18 C 0.6459(3) 0.4603(10) 0.68045(17) 0.0589(11) Uani 1 1 d . . . . .
C19 C 0.6488(3) 0.3250(11) 0.63435(19) 0.0821(15) Uani 1 1 d . . . . .
H19 H 0.606632 0.189060 0.620252 0.099 Uiso 1 1 calc R U . . .
C20 C 0.7128(4) 0.3852(11) 0.60824(19) 0.0852(16) Uani 1 1 d . . . . .
H20 H 0.713099 0.287620 0.577315 0.102 Uiso 1 1 calc R U . . .
C21 C 0.5776(3) 0.3898(11) 0.70868(18) 0.0704(13) Uani 1 1 d . . . . .
H21A H 0.571712 0.185188 0.709988 0.084 Uiso 1 1 calc R U . . .
H21B H 0.596374 0.458498 0.744855 0.084 Uiso 1 1 calc R U . . .
O1S O 0.491(2) 0.519(5) 0.5384(11) 0.189(9) Uiso 0.225(4) 1 d D U P A -1
O2S O 0.513(2) 1.176(5) 0.4708(11) 0.189(9) Uiso 0.225(4) 1 d D U P A -1
C1S C 0.480(3) 0.224(5) 0.5176(17) 0.189(9) Uiso 0.225(4) 1 d D U P A -1
H1SA H 0.509004 0.094337 0.544841 0.284 Uiso 0.225(4) 1 calc R U P A -1
H1SB H 0.504410 0.207352 0.487694 0.284 Uiso 0.225(4) 1 calc DR U P A -1
H1SC H 0.418492 0.178339 0.506884 0.284 Uiso 0.225(4) 1 calc R U P A -1
C2S C 0.494(2) 0.703(5) 0.4964(13) 0.189(9) Uiso 0.225(4) 1 d D U P A -1
H2SA H 0.440167 0.689421 0.468772 0.227 Uiso 0.225(4) 1 calc R U P A -1
H2SB H 0.542106 0.647966 0.481298 0.227 Uiso 0.225(4) 1 calc R U P A -1
C3S C 0.508(3) 1.002(5) 0.5158(12) 0.189(9) Uiso 0.225(4) 1 d D U P A -1
H3SA H 0.458790 1.062235 0.529393 0.227 Uiso 0.225(4) 1 calc R U P A -1
H3SB H 0.560996 1.017072 0.543962 0.227 Uiso 0.225(4) 1 calc R U P A -1
C4S C 0.525(3) 1.464(5) 0.4886(17) 0.189(9) Uiso 0.225(4) 1 d D U P A -1
H4SA H 0.544347 1.576146 0.462804 0.284 Uiso 0.225(4) 1 calc R U P A -1
H4SB H 0.569037 1.472060 0.521819 0.284 Uiso 0.225(4) 1 calc R U P A -1
H4SC H 0.471155 1.538399 0.493064 0.284 Uiso 0.225(4) 1 calc R U P A -1


_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
O1 C1 1.233(5) . ?
N1 H1 0.92(5) . ?
N1 C1 1.350(5) . ?
N1 C21 1.450(6) 3_666 ?
N2 H2 0.87(5) . ?
N2 C1 1.344(5) . ?
N2 C2 1.452(5) . ?
N3 C6 1.423(5) . ?
N3 C9 1.416(5) . ?
N3 C15 1.416(5) . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?
C2 C3 1.502(6) . ?
C3 C4 1.377(6) . ?
C3 C8 1.383(6) . ?
C4 H4 0.9300 . ?
C4 C5 1.374(6) . ?
C5 H5 0.9300 . ?
C5 C6 1.363(6) . ?
C6 C7 1.375(6) . ?
C7 H7 0.9300 . ?
C7 C8 1.377(6) . ?
C8 H8 0.9300 . ?
C9 C10 1.365(7) . ?
C9 C14 1.373(6) . ?
C10 H10 0.9300 . ?
C10 C11 1.369(8) . ?
C11 H11 0.9300 . ?
C11 C12 1.357(10) . ?
C12 H12 0.9300 . ?
C12 C13 1.347(10) . ?
C13 H13 0.9300 . ?
C13 C14 1.374(8) . ?
C14 H14 0.9300 . ?
C15 C16 1.378(6) . ?
C15 C20 1.371(6) . ?
C16 H16 0.9300 . ?
C16 C17 1.382(6) . ?
C17 H17 0.9300 . ?
C17 C18 1.367(6) . ?
C18 C19 1.372(6) . ?
C18 C21 1.492(6) . ?
C19 H19 0.9300 . ?
C19 C20 1.384(6) . ?
C20 H20 0.9300 . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
O1S C1S 1.489(15) . ?
O1S C2S 1.408(15) . ?
O2S C3S 1.453(15) . ?
O2S C4S 1.434(15) . ?
C1S H1SA 0.9600 . ?
C1S H1SB 0.9600 . ?
C1S H1SC 0.9600 . ?
C2S H2SA 0.9700 . ?
C2S H2SB 0.9700 . ?
C2S C3S 1.491(15) . ?
C3S H3SA 0.9700 . ?
C3S H3SB 0.9700 . ?
C4S H4SA 0.9600 . ?
C4S H4SB 0.9600 . ?
C4S H4SC 0.9600 . ?

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
C1 N1 H1 120(3) . . ?
C1 N1 C21 124.0(4) . 3_666 ?
C21 N1 H1 115(3) 3_666 . ?
C1 N2 H2 119(3) . . ?
C1 N2 C2 122.2(4) . . ?
C2 N2 H2 119(3) . . ?
C9 N3 C6 120.1(4) . . ?
C9 N3 C15 120.2(4) . . ?
C15 N3 C6 119.6(3) . . ?
O1 C1 N1 122.5(4) . . ?
O1 C1 N2 122.9(4) . . ?
N2 C1 N1 114.6(4) . . ?
N2 C2 H2A 108.7 . . ?
N2 C2 H2B 108.7 . . ?
N2 C2 C3 114.2(3) . . ?
H2A C2 H2B 107.6 . . ?
C3 C2 H2A 108.7 . . ?
C3 C2 H2B 108.7 . . ?
C4 C3 C2 122.7(4) . . ?
C4 C3 C8 116.1(4) . . ?
C8 C3 C2 121.2(4) . . ?
C3 C4 H4 118.8 . . ?
C5 C4 C3 122.4(4) . . ?
C5 C4 H4 118.8 . . ?
C4 C5 H5 119.7 . . ?
C6 C5 C4 120.7(4) . . ?
C6 C5 H5 119.7 . . ?
C5 C6 N3 122.0(4) . . ?
C5 C6 C7 118.2(4) . . ?
C7 C6 N3 119.8(4) . . ?
C6 C7 H7 119.6 . . ?
C6 C7 C8 120.8(4) . . ?
C8 C7 H7 119.6 . . ?
C3 C8 H8 119.1 . . ?
C7 C8 C3 121.7(4) . . ?
C7 C8 H8 119.1 . . ?
C10 C9 N3 120.5(4) . . ?
C10 C9 C14 118.7(5) . . ?
C14 C9 N3 120.8(4) . . ?
C9 C10 H10 119.8 . . ?
C9 C10 C11 120.5(6) . . ?
C11 C10 H10 119.8 . . ?
C10 C11 H11 119.6 . . ?
C12 C11 C10 120.8(7) . . ?
C12 C11 H11 119.6 . . ?
C11 C12 H12 120.6 . . ?
C13 C12 C11 118.9(6) . . ?
C13 C12 H12 120.6 . . ?
C12 C13 H13 119.3 . . ?
C12 C13 C14 121.4(7) . . ?
C14 C13 H13 119.3 . . ?
C9 C14 C13 119.7(6) . . ?
C9 C14 H14 120.2 . . ?
C13 C14 H14 120.2 . . ?
C16 C15 N3 122.0(4) . . ?
C20 C15 N3 120.7(4) . . ?
C20 C15 C16 117.3(4) . . ?
C15 C16 H16 119.5 . . ?
C15 C16 C17 121.0(4) . . ?
C17 C16 H16 119.5 . . ?
C16 C17 H17 119.0 . . ?
C18 C17 C16 122.1(4) . . ?
C18 C17 H17 119.0 . . ?
C17 C18 C19 116.7(4) . . ?
C17 C18 C21 122.0(4) . . ?
C19 C18 C21 121.3(4) . . ?
C18 C19 H19 119.1 . . ?
C18 C19 C20 121.9(4) . . ?
C20 C19 H19 119.1 . . ?
C15 C20 C19 121.1(4) . . ?
C15 C20 H20 119.5 . . ?
C19 C20 H20 119.5 . . ?
N1 C21 C18 112.9(4) 3_666 . ?
N1 C21 H21A 109.0 3_666 . ?
N1 C21 H21B 109.0 3_666 . ?
C18 C21 H21A 109.0 . . ?
C18 C21 H21B 109.0 . . ?
H21A C21 H21B 107.8 . . ?
C2S O1S C1S 108.5(16) . . ?
C4S O2S C3S 107.8(16) . . ?
O1S C1S H1SA 109.5 . . ?
O1S C1S H1SB 109.5 . . ?
O1S C1S H1SC 109.5 . . ?
H1SA C1S H1SB 109.5 . . ?
H1SA C1S H1SC 109.5 . . ?
H1SB C1S H1SC 109.5 . . ?
O1S C2S H2SA 109.6 . . ?
O1S C2S H2SB 109.6 . . ?
O1S C2S C3S 110.2(17) . . ?
H2SA C2S H2SB 108.1 . . ?
C3S C2S H2SA 109.6 . . ?
C3S C2S H2SB 109.6 . . ?
O2S C3S C2S 106.8(16) . . ?
O2S C3S H3SA 110.4 . . ?
O2S C3S H3SB 110.4 . . ?
C2S C3S H3SA 110.4 . . ?
C2S C3S H3SB 110.4 . . ?
H3SA C3S H3SB 108.6 . . ?
O2S C4S H4SA 109.5 . . ?
O2S C4S H4SB 109.5 . . ?
O2S C4S H4SC 109.5 . . ?
H4SA C4S H4SB 109.5 . . ?
H4SA C4S H4SC 109.5 . . ?
H4SB C4S H4SC 109.5 . . ?

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
N2 C2 C3 C4 125.0(5) . . . . ?
N2 C2 C3 C8 -54.4(6) . . . . ?
N3 C6 C7 C8 -177.6(4) . . . . ?
N3 C9 C10 C11 179.0(5) . . . . ?
N3 C9 C14 C13 -178.4(5) . . . . ?
N3 C15 C16 C17 -179.1(4) . . . . ?
N3 C15 C20 C19 -179.4(5) . . . . ?
C1 N2 C2 C3 98.3(5) . . . . ?
C2 N2 C1 O1 0.6(6) . . . . ?
C2 N2 C1 N1 -179.3(3) . . . . ?
C2 C3 C4 C5 -178.8(5) . . . . ?
C2 C3 C8 C7 179.4(4) . . . . ?
C3 C4 C5 C6 -0.4(8) . . . . ?
C4 C3 C8 C7 -0.1(7) . . . . ?
C4 C5 C6 N3 178.0(5) . . . . ?
C4 C5 C6 C7 -0.4(8) . . . . ?
C5 C6 C7 C8 1.0(8) . . . . ?
C6 N3 C9 C10 38.1(7) . . . . ?
C6 N3 C9 C14 -142.5(5) . . . . ?
C6 N3 C15 C16 -142.9(5) . . . . ?
C6 N3 C15 C20 36.5(7) . . . . ?
C6 C7 C8 C3 -0.7(8) . . . . ?
C8 C3 C4 C5 0.6(7) . . . . ?
C9 N3 C6 C5 40.9(7) . . . . ?
C9 N3 C6 C7 -140.7(5) . . . . ?
C9 N3 C15 C16 39.9(6) . . . . ?
C9 N3 C15 C20 -140.7(5) . . . . ?
C9 C10 C11 C12 -0.2(11) . . . . ?
C10 C9 C14 C13 1.1(8) . . . . ?
C10 C11 C12 C13 0.2(11) . . . . ?
C11 C12 C13 C14 0.4(11) . . . . ?
C12 C13 C14 C9 -1.1(10) . . . . ?
C14 C9 C10 C11 -0.4(9) . . . . ?
C15 N3 C6 C5 -136.3(5) . . . . ?
C15 N3 C6 C7 42.1(6) . . . . ?
C15 N3 C9 C10 -144.8(5) . . . . ?
C15 N3 C9 C14 34.6(7) . . . . ?
C15 C16 C17 C18 -2.2(8) . . . . ?
C16 C15 C20 C19 0.0(8) . . . . ?
C16 C17 C18 C19 1.4(7) . . . . ?
C16 C17 C18 C21 -179.6(4) . . . . ?
C17 C18 C19 C20 0.1(8) . . . . ?
C17 C18 C21 N1 104.3(5) . . . 3_666 ?
C18 C19 C20 C15 -0.8(9) . . . . ?
C19 C18 C21 N1 -76.7(6) . . . 3_666 ?
C20 C15 C16 C17 1.5(7) . . . . ?
C21 N1 C1 O1 6.1(6) 3_666 . . . ?
C21 N1 C1 N2 -174.0(4) 3_666 . . . ?
C21 C18 C19 C20 -178.9(5) . . . . ?
O1S C2S C3S O2S 178.0(14) . . . . ?
C1S O1S C2S C3S -178.9(14) . . . . ?
C4S O2S C3S C2S 179.7(17) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
# start Validation Reply Form
_vrf_THETM01_tpah_dme            
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: Weakly diffracting, thin needle crystal. No significant diffraction
intensity observed above d = 0.90 Angstroms (2th = 46.5 degrees) despite very
slow data collection scan rate. The dataset was therefore truncated at
d = 0.9 A at which value the mean I/sig(I) value fell below 1.5.
;
####################################################################### 
# 
# 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_mfi_brmc_tegme
_database_code_depnum_ccdc_archive 'CCDC 2344713'
loop_
_audit_author_name
_audit_author_address
'Mark D. Smith'
;University of South Carolina
United States of America
;
_audit_update_record             
;
2024-03-31 deposited with the CCDC.	2024-10-02 downloaded from the CCDC.
;
_audit_creation_date             2021-11-30
_audit_creation_method           
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C42 H36 Br2 N6 O2, 0.716(C2 H6 O S)'
_chemical_formula_sum            'C43.43 H40.29 Br2 N6 O2.72 S0.71'
_chemical_formula_weight         872.45
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.878(2)
_cell_length_b                   4.6413(6)
_cell_length_c                   26.735(3)
_cell_angle_alpha                90
_cell_angle_beta                 99.584(3)
_cell_angle_gamma                90
_cell_volume                     1942.8(4)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    8762
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.271
_cell_measurement_theta_min      2.602
_shelx_estimated_absorpt_T_max   0.958
_shelx_estimated_absorpt_T_min   0.751
_exptl_absorpt_coefficient_mu    2.173
_exptl_absorpt_correction_T_max  0.5624
_exptl_absorpt_correction_T_min  0.4717
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0854 before and 0.0590 after correction.
The Ratio of minimum to maximum transmission is 0.8387.
The λ/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.491
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             892
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_diffrn_reflns_av_R_equivalents  0.0641
_diffrn_reflns_av_unetI/netI     0.0427
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            26749
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.374
_diffrn_reflns_theta_min         1.847
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 PHOTON-II
_diffrn_detector_area_resol_mean 7.39
_diffrn_detector_type            'area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          X-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3335
_reflns_number_total             3961
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'Bruker APEX3 v2019.1-0 (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_refine_diff_density_max         0.456
_refine_diff_density_min         -1.061
_refine_diff_density_rms         0.088
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.222
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         3961
_refine_ls_number_restraints     14
_refine_ls_R_factor_all          0.0823
_refine_ls_R_factor_gt           0.0667
_refine_ls_restrained_S_all      1.233
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0001P)²+7.7180P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1120
_refine_ls_wR_factor_ref         0.1168
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All N(H) groups
2. Restrained distances
 S1S-O1S
 1.5 with sigma of 0.015
 S1S-C1S = S1S-C2S
 1.775 with sigma of 0.02
 S2S-O2S
 1.5 with sigma of 0.015
 S2S-C3S = S2S-C4S
 1.775 with sigma of 0.02
 N1-H1 = N2-H2
 0.85 with sigma of 0.02
 O1S-C1S = O1S-C2S
 2.623 with sigma of 0.04
 C1S-C2S
 2.66 with sigma of 0.04
 O2S-C3S = O2S-C4S
 2.623 with sigma of 0.04
 C3S-C4S
 2.66 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uiso(C2S) = Uiso(O2S)
4. Others
 Sof(S1S)=Sof(O1S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2S)=Sof(H2SA)=
 Sof(H2SB)=Sof(H2SC)=FVAR(1)
 Sof(S2S)=Sof(O2S)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(H3SC)=Sof(C4S)=Sof(H4SA)=
 Sof(H4SB)=Sof(H4SC)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C21(H21A,H21B)
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C10(H10), C11(H11), C13(H13), C14(H14),
 C16(H16), C17(H17), C19(H19), C20(H20)
5.c Idealised Me refined with riding coordinates:
 C1S(H1SA,H1SB,H1SC), C2S(H2SA,H2SB,H2SC), C3S(H3SA,H3SB,H3SC), C4S(H4SA,H4SB,
 H4SC)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
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 1.17616(3) 0.83659(13) 0.72035(2) 0.03605(15) Uani 1 1 d . . . . .
O1 O 0.6006(2) 0.9245(6) 0.33819(12) 0.0305(8) Uani 1 1 d . . . . .
N1 N 0.5333(3) 0.4971(9) 0.31956(16) 0.0298(9) Uani 1 1 d D . . . .
H1 H 0.541(3) 0.317(5) 0.322(2) 0.045 Uiso 1 1 d D U . . .
N2 N 0.6723(2) 0.5079(8) 0.35886(15) 0.0256(9) Uani 1 1 d D . . . .
H2 H 0.666(3) 0.327(5) 0.3594(19) 0.038 Uiso 1 1 d D U . . .
N3 N 0.8232(2) 0.6479(11) 0.59653(14) 0.0356(10) Uani 1 1 d . . . . .
C1 C 0.6020(3) 0.6536(10) 0.33876(15) 0.0217(9) Uani 1 1 d . . . . .
C2 C 0.7530(3) 0.6415(11) 0.37881(16) 0.0269(10) Uani 1 1 d . . . . .
H2A H 0.752650 0.841254 0.365779 0.032 Uiso 1 1 calc R U . . .
H2B H 0.799061 0.535740 0.365886 0.032 Uiso 1 1 calc R U . . .
C3 C 0.7733(3) 0.6498(10) 0.43587(15) 0.0245(9) Uani 1 1 d . . . . .
C4 C 0.8477(3) 0.5319(11) 0.46237(17) 0.0294(11) Uani 1 1 d . . . . .
H4 H 0.887974 0.448947 0.444033 0.035 Uiso 1 1 calc R U . . .
C5 C 0.8649(3) 0.5317(11) 0.51495(17) 0.0299(11) Uani 1 1 d . . . . .
H5 H 0.916363 0.448161 0.532011 0.036 Uiso 1 1 calc R U . . .
C6 C 0.8084(3) 0.6507(12) 0.54245(16) 0.0313(11) Uani 1 1 d . . . . .
C7 C 0.7340(3) 0.7715(13) 0.51649(18) 0.0434(15) Uani 1 1 d . . . . .
H7 H 0.694168 0.856906 0.534871 0.052 Uiso 1 1 calc R U . . .
C8 C 0.7173(3) 0.7690(11) 0.46405(18) 0.0379(13) Uani 1 1 d . . . . .
H8 H 0.665643 0.851906 0.447051 0.045 Uiso 1 1 calc R U . . .
C9 C 0.9068(3) 0.6851(11) 0.62400(16) 0.0280(10) Uani 1 1 d . . . . .
C10 C 0.9636(3) 0.8724(12) 0.60743(18) 0.0389(13) Uani 1 1 d . . . . .
H10 H 0.947133 0.973380 0.576436 0.047 Uiso 1 1 calc R U . . .
C11 C 1.0443(3) 0.9155(11) 0.63532(18) 0.0354(12) Uani 1 1 d . . . . .
H11 H 1.082752 1.047169 0.623889 0.043 Uiso 1 1 calc R U . . .
C12 C 1.0678(3) 0.7657(10) 0.67962(16) 0.0267(10) Uani 1 1 d . . . . .
C13 C 1.0136(3) 0.5729(11) 0.69639(16) 0.0301(11) Uani 1 1 d . . . . .
H13 H 1.030977 0.469289 0.727010 0.036 Uiso 1 1 calc R U . . .
C14 C 0.9330(3) 0.5302(12) 0.66826(17) 0.0322(11) Uani 1 1 d . . . . .
H14 H 0.895429 0.393927 0.679346 0.039 Uiso 1 1 calc R U . . .
C15 C 0.7545(3) 0.5897(10) 0.62310(17) 0.0288(11) Uani 1 1 d . . . . .
C16 C 0.7470(3) 0.7339(11) 0.66713(17) 0.0309(11) Uani 1 1 d . . . . .
H16 H 0.787251 0.878837 0.679733 0.037 Uiso 1 1 calc R U . . .
C17 C 0.6805(3) 0.6677(12) 0.69327(17) 0.0345(11) Uani 1 1 d . . . . .
H17 H 0.676513 0.767391 0.723818 0.041 Uiso 1 1 calc R U . . .
C18 C 0.6200(3) 0.4592(10) 0.67566(17) 0.0271(10) Uani 1 1 d . . . . .
C19 C 0.6274(4) 0.3228(14) 0.6305(2) 0.0508(15) Uani 1 1 d . . . . .
H19 H 0.586185 0.182710 0.617020 0.061 Uiso 1 1 calc R U . . .
C20 C 0.6936(4) 0.3872(13) 0.6049(2) 0.0504(16) Uani 1 1 d . . . . .
H20 H 0.697276 0.289885 0.574055 0.060 Uiso 1 1 calc R U . . .
C21 C 0.5483(3) 0.3876(11) 0.70374(17) 0.0300(11) Uani 1 1 d . . . . .
H21A H 0.543493 0.175488 0.705984 0.036 Uiso 1 1 calc R U . . .
H21B H 0.562426 0.463383 0.738751 0.036 Uiso 1 1 calc R U . . .
S1S S 0.4736(6) 0.898(2) 0.4915(4) 0.089(3) Uiso 0.268(6) 1 d D . P A -1
O1S O 0.4855(11) 1.198(3) 0.4902(6) 0.056(5) Uiso 0.268(6) 1 d D . P A -1
C1S C 0.5256(17) 0.613(5) 0.4671(9) 0.074(8) Uiso 0.268(6) 1 d D . P A -1
H1SA H 0.587322 0.630221 0.478558 0.112 Uiso 0.268(6) 1 calc R U P A -1
H1SB H 0.513317 0.618435 0.430002 0.112 Uiso 0.268(6) 1 calc R U P A -1
H1SC H 0.505368 0.430372 0.479170 0.112 Uiso 0.268(6) 1 calc R U P A -1
C2S C 0.472(2) 0.761(7) 0.5527(8) 0.088(8) Uiso 0.268(6) 1 d D . P A -1
H2SA H 0.459198 0.917014 0.574971 0.133 Uiso 0.268(6) 1 calc R U P A -1
H2SB H 0.528062 0.678414 0.566257 0.133 Uiso 0.268(6) 1 calc R U P A -1
H2SC H 0.428225 0.611267 0.551010 0.133 Uiso 0.268(6) 1 calc R U P A -1
S2S S 0.4575(14) 0.651(6) 0.4970(8) 0.071(8) Uiso 0.090(6) 1 d D . P B -2
O2S O 0.478(4) 0.665(14) 0.5537(9) 0.088(8) Uiso 0.090(6) 1 d D . P B -2
C3S C 0.512(5) 0.940(11) 0.473(3) 0.07(2) Uiso 0.090(6) 1 d D . P B -2
H3SA H 0.478542 1.009884 0.441293 0.106 Uiso 0.090(6) 1 calc R U P B -2
H3SB H 0.568003 0.873061 0.466697 0.106 Uiso 0.090(6) 1 calc R U P B -2
H3SC H 0.520332 1.097106 0.497912 0.106 Uiso 0.090(6) 1 calc R U P B -2
C4S C 0.519(4) 0.370(10) 0.476(2) 0.043(17) Uiso 0.090(6) 1 d D . P B -2
H4SA H 0.485689 0.191024 0.473482 0.064 Uiso 0.090(6) 1 calc R U P B -2
H4SB H 0.571411 0.343844 0.500911 0.064 Uiso 0.090(6) 1 calc R U P B -2
H4SC H 0.533355 0.419838 0.443181 0.064 Uiso 0.090(6) 1 calc R U P B -2


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 C12 1.906(5) . ?
O1 C1 1.257(5) . ?
N1 H1 0.85(2) . ?
N1 C1 1.339(6) . ?
N1 C21 1.443(6) 3_666 ?
N2 H2 0.85(2) . ?
N2 C1 1.339(6) . ?
N2 C2 1.443(6) . ?
N3 C6 1.426(6) . ?
N3 C9 1.417(6) . ?
N3 C15 1.423(6) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C2 C3 1.506(6) . ?
C3 C4 1.385(6) . ?
C3 C8 1.374(6) . ?
C4 H4 0.9500 . ?
C4 C5 1.387(6) . ?
C5 H5 0.9500 . ?
C5 C6 1.367(7) . ?
C6 C7 1.385(7) . ?
C7 H7 0.9500 . ?
C7 C8 1.383(7) . ?
C8 H8 0.9500 . ?
C9 C10 1.377(7) . ?
C9 C14 1.388(6) . ?
C10 H10 0.9500 . ?
C10 C11 1.386(7) . ?
C11 H11 0.9500 . ?
C11 C12 1.371(6) . ?
C12 C13 1.368(7) . ?
C13 H13 0.9500 . ?
C13 C14 1.386(6) . ?
C14 H14 0.9500 . ?
C15 C16 1.376(6) . ?
C15 C20 1.378(7) . ?
C16 H16 0.9500 . ?
C16 C17 1.394(7) . ?
C17 H17 0.9500 . ?
C17 C18 1.390(7) . ?
C18 C19 1.384(7) . ?
C18 C21 1.501(6) . ?
C19 H19 0.9500 . ?
C19 C20 1.381(8) . ?
C20 H20 0.9500 . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
S1S O1S 1.405(12) . ?
S1S C1S 1.743(16) . ?
S1S C2S 1.759(16) . ?
C1S H1SA 0.9800 . ?
C1S H1SB 0.9800 . ?
C1S H1SC 0.9800 . ?
C2S H2SA 0.9800 . ?
C2S H2SB 0.9800 . ?
C2S H2SC 0.9800 . ?
S2S O2S 1.498(15) . ?
S2S C3S 1.77(2) . ?
S2S C4S 1.771(19) . ?
C3S H3SA 0.9800 . ?
C3S H3SB 0.9800 . ?
C3S H3SC 0.9800 . ?
C4S H4SA 0.9800 . ?
C4S H4SB 0.9800 . ?
C4S H4SC 0.9800 . ?

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
C1 N1 H1 115(4) . . ?
C1 N1 C21 125.4(4) . 3_666 ?
C21 N1 H1 120(4) 3_666 . ?
C1 N2 H2 114(4) . . ?
C1 N2 C2 124.1(4) . . ?
C2 N2 H2 121(4) . . ?
C9 N3 C6 120.4(4) . . ?
C9 N3 C15 119.6(4) . . ?
C15 N3 C6 119.8(4) . . ?
O1 C1 N1 121.7(4) . . ?
O1 C1 N2 121.4(4) . . ?
N1 C1 N2 116.8(4) . . ?
N2 C2 H2A 108.7 . . ?
N2 C2 H2B 108.7 . . ?
N2 C2 C3 114.3(4) . . ?
H2A C2 H2B 107.6 . . ?
C3 C2 H2A 108.7 . . ?
C3 C2 H2B 108.7 . . ?
C4 C3 C2 121.9(4) . . ?
C8 C3 C2 121.1(4) . . ?
C8 C3 C4 117.0(4) . . ?
C3 C4 H4 119.1 . . ?
C3 C4 C5 121.7(4) . . ?
C5 C4 H4 119.1 . . ?
C4 C5 H5 119.7 . . ?
C6 C5 C4 120.6(4) . . ?
C6 C5 H5 119.7 . . ?
C5 C6 N3 122.0(4) . . ?
C5 C6 C7 118.4(4) . . ?
C7 C6 N3 119.6(4) . . ?
C6 C7 H7 119.7 . . ?
C8 C7 C6 120.6(5) . . ?
C8 C7 H7 119.7 . . ?
C3 C8 C7 121.8(5) . . ?
C3 C8 H8 119.1 . . ?
C7 C8 H8 119.1 . . ?
C10 C9 N3 121.1(4) . . ?
C10 C9 C14 118.8(4) . . ?
C14 C9 N3 120.0(4) . . ?
C9 C10 H10 119.5 . . ?
C9 C10 C11 120.9(4) . . ?
C11 C10 H10 119.5 . . ?
C10 C11 H11 120.5 . . ?
C12 C11 C10 119.1(5) . . ?
C12 C11 H11 120.5 . . ?
C11 C12 Br1 119.8(4) . . ?
C13 C12 Br1 118.9(3) . . ?
C13 C12 C11 121.3(4) . . ?
C12 C13 H13 120.3 . . ?
C12 C13 C14 119.3(4) . . ?
C14 C13 H13 120.3 . . ?
C9 C14 H14 119.8 . . ?
C13 C14 C9 120.5(5) . . ?
C13 C14 H14 119.8 . . ?
C16 C15 N3 121.1(4) . . ?
C16 C15 C20 118.6(5) . . ?
C20 C15 N3 120.3(4) . . ?
C15 C16 H16 119.9 . . ?
C15 C16 C17 120.1(5) . . ?
C17 C16 H16 119.9 . . ?
C16 C17 H17 119.2 . . ?
C18 C17 C16 121.5(4) . . ?
C18 C17 H17 119.2 . . ?
C17 C18 C21 121.6(4) . . ?
C19 C18 C17 117.3(5) . . ?
C19 C18 C21 121.1(4) . . ?
C18 C19 H19 119.5 . . ?
C20 C19 C18 121.1(5) . . ?
C20 C19 H19 119.5 . . ?
C15 C20 C19 121.3(5) . . ?
C15 C20 H20 119.3 . . ?
C19 C20 H20 119.3 . . ?
N1 C21 C18 113.7(4) 3_666 . ?
N1 C21 H21A 108.8 3_666 . ?
N1 C21 H21B 108.8 3_666 . ?
C18 C21 H21A 108.8 . . ?
C18 C21 H21B 108.8 . . ?
H21A C21 H21B 107.7 . . ?
O1S S1S C1S 132.0(13) . . ?
O1S S1S C2S 113.9(13) . . ?
C1S S1S C2S 98.8(14) . . ?
S1S C1S H1SA 109.5 . . ?
S1S C1S H1SB 109.5 . . ?
S1S C1S H1SC 109.5 . . ?
H1SA C1S H1SB 109.5 . . ?
H1SA C1S H1SC 109.5 . . ?
H1SB C1S H1SC 109.5 . . ?
S1S C2S H2SA 109.5 . . ?
S1S C2S H2SB 109.5 . . ?
S1S C2S H2SC 109.5 . . ?
H2SA C2S H2SB 109.5 . . ?
H2SA C2S H2SC 109.5 . . ?
H2SB C2S H2SC 109.5 . . ?
O2S S2S C3S 107(2) . . ?
O2S S2S C4S 108(2) . . ?
C4S S2S C3S 96.7(19) . . ?
S2S C3S H3SA 109.5 . . ?
S2S C3S H3SB 109.5 . . ?
S2S C3S H3SC 109.5 . . ?
H3SA C3S H3SB 109.5 . . ?
H3SA C3S H3SC 109.5 . . ?
H3SB C3S H3SC 109.5 . . ?
S2S C4S H4SA 109.5 . . ?
S2S C4S H4SB 109.5 . . ?
S2S C4S H4SC 109.5 . . ?
H4SA C4S H4SB 109.5 . . ?
H4SA C4S H4SC 109.5 . . ?
H4SB C4S H4SC 109.5 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N1 H1 O1 0.85(2) 2.07(3) 2.877(5) 160(5) 1_545 yes
N2 H2 O1 0.85(2) 2.17(3) 2.954(5) 155(5) 1_545 yes

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
Br1 C12 C13 C14 176.9(4) . . . . ?
N2 C2 C3 C4 123.8(5) . . . . ?
N2 C2 C3 C8 -54.5(7) . . . . ?
N3 C6 C7 C8 -178.1(5) . . . . ?
N3 C9 C10 C11 177.8(5) . . . . ?
N3 C9 C14 C13 -177.6(5) . . . . ?
N3 C15 C16 C17 -178.2(5) . . . . ?
N3 C15 C20 C19 178.7(6) . . . . ?
C1 N2 C2 C3 104.3(5) . . . . ?
C2 N2 C1 O1 -3.6(7) . . . . ?
C2 N2 C1 N1 176.7(4) . . . . ?
C2 C3 C4 C5 -177.9(5) . . . . ?
C2 C3 C8 C7 178.3(5) . . . . ?
C3 C4 C5 C6 -0.4(8) . . . . ?
C4 C3 C8 C7 -0.1(8) . . . . ?
C4 C5 C6 N3 178.5(5) . . . . ?
C4 C5 C6 C7 -0.2(8) . . . . ?
C5 C6 C7 C8 0.6(9) . . . . ?
C6 N3 C9 C10 37.2(7) . . . . ?
C6 N3 C9 C14 -142.4(5) . . . . ?
C6 N3 C15 C16 -141.7(5) . . . . ?
C6 N3 C15 C20 38.0(7) . . . . ?
C6 C7 C8 C3 -0.4(9) . . . . ?
C8 C3 C4 C5 0.5(8) . . . . ?
C9 N3 C6 C5 37.3(8) . . . . ?
C9 N3 C6 C7 -144.1(5) . . . . ?
C9 N3 C15 C16 42.2(7) . . . . ?
C9 N3 C15 C20 -138.1(5) . . . . ?
C9 C10 C11 C12 0.9(8) . . . . ?
C10 C9 C14 C13 2.8(7) . . . . ?
C10 C11 C12 Br1 -176.7(4) . . . . ?
C10 C11 C12 C13 0.7(8) . . . . ?
C11 C12 C13 C14 -0.6(7) . . . . ?
C12 C13 C14 C9 -1.2(7) . . . . ?
C14 C9 C10 C11 -2.7(8) . . . . ?
C15 N3 C6 C5 -138.8(5) . . . . ?
C15 N3 C6 C7 39.8(8) . . . . ?
C15 N3 C9 C10 -146.7(5) . . . . ?
C15 N3 C9 C14 33.7(7) . . . . ?
C15 C16 C17 C18 -0.7(8) . . . . ?
C16 C15 C20 C19 -1.6(9) . . . . ?
C16 C17 C18 C19 -1.1(8) . . . . ?
C16 C17 C18 C21 -180.0(4) . . . . ?
C17 C18 C19 C20 1.6(9) . . . . ?
C17 C18 C21 N1 104.7(5) . . . 3_666 ?
C18 C19 C20 C15 -0.2(10) . . . . ?
C19 C18 C21 N1 -74.2(6) . . . 3_666 ?
C20 C15 C16 C17 2.1(7) . . . . ?
C21 N1 C1 O1 0.4(7) 3_666 . . . ?
C21 N1 C1 N2 -179.9(4) 3_666 . . . ?
C21 C18 C19 C20 -179.5(5) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
