# Supplementary Information (SI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2025

####################################################################### 
# 
# 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_dbr34
_database_code_depnum_ccdc_archive 'CCDC 2384641'
loop_
_audit_author_name
_audit_author_address
'Raghavaiah Pallepogu'
;Central University of Karnataka
India
;
_audit_update_record             
;
2024-09-17 deposited with the CCDC.	2025-01-13 downloaded from the CCDC.
;
_audit_creation_date             2021-12-11
_audit_creation_method           
;
Olex2 1.3-ac4
(compiled 2018.12.18 svn.r3554 for Rigaku Oxford Diffraction, GUI svn.r1)
;
_shelx_SHELXL_version_number     2018/1
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C22 H16 N4 S'
_chemical_formula_sum            'C22 H16 N4 S'
_chemical_formula_weight         368.45
_chemical_absolute_configuration ?
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C H N O S'
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'
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      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   5.8739(2)
_cell_length_b                   12.2152(6)
_cell_length_c                   25.4655(13)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1827.17(14)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    4329
_cell_measurement_temperature    297.5(4)
_cell_measurement_theta_max      22.9330
_cell_measurement_theta_min      2.2870
_shelx_estimated_absorpt_T_max   0.981
_shelx_estimated_absorpt_T_min   0.963
_exptl_absorpt_coefficient_mu    0.191
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38026
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             768
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1186
_diffrn_reflns_av_unetI/netI     0.0907
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            10250
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.310
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      297.5(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -61.00  97.00   0.50   12.50    --   16.22  11.00   8.00  316
  2  ω     20.00  60.00   0.50   12.50    --   16.22-143.00 -38.00   80
  3  ω    -29.00   7.00   0.50   12.50    --  -14.97 -45.00 -90.00   72
  4  ω    -53.00   6.00   0.50   12.50    --   16.22 -45.00 -90.00  118
  5  ω    -85.00 -38.00   0.50   12.50    --  -14.97 -45.00 -90.00   94
  6  ω    -36.00 -10.00   0.50   12.50    --   16.22 -94.00-180.00   52
  7  ω    -90.00 -28.00   0.50   12.50    --  -14.97 159.00 -85.00  124
  8  ω    -36.00 -11.00   0.50   12.50    --  -14.97 125.00 150.00   50
  9  ω    -69.00 -41.00   0.50   12.50    --  -14.97 125.00 150.00   56
 10  ω     11.00  69.00   0.50   12.50    --   16.22-125.00 150.00  116
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0053586000
_diffrn_orient_matrix_UB_12      0.0568135000
_diffrn_orient_matrix_UB_13      0.0056160000
_diffrn_orient_matrix_UB_21      0.0199551000
_diffrn_orient_matrix_UB_22      -0.0111650000
_diffrn_orient_matrix_UB_23      0.0269520000
_diffrn_orient_matrix_UB_31      0.1189550000
_diffrn_orient_matrix_UB_32      0.0044203000
_diffrn_orient_matrix_UB_33      -0.0042474000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_reflns_Friedel_coverage         0.685
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     0.976
_reflns_number_gt                1866
_reflns_number_total             3183
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.160
_refine_diff_density_min         -0.284
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details 
;
 Flack x determined using 528 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(10)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.907
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         3183
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0947
_refine_ls_R_factor_gt           0.0557
_refine_ls_restrained_S_all      0.907
_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)+(0.0310P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0896
_refine_ls_wR_factor_ref         0.1083
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C5(H5), C13(H13), C22(H22), C16(H16), C2(H2), C3(H3), C14(H14),
 C18(H18), C4(H4), C15(H15), C19(H19), C20(H20), C21(H21)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
S1 S 0.8300(2) 0.77278(12) 0.71185(6) 0.0793(5) Uani 1 1 d . . . . .
N2 N 0.4533(7) 0.4550(3) 0.63987(16) 0.0637(12) Uani 1 1 d . . . . .
N1 N 0.4441(6) 0.8048(3) 0.66454(16) 0.0644(11) Uani 1 1 d . . . . .
N3 N 0.6445(8) 0.4407(4) 0.66922(17) 0.0754(12) Uani 1 1 d . . . . .
N4 N 0.7073(7) 0.5374(4) 0.68535(17) 0.0749(13) Uani 1 1 d . . . . .
C11 C 0.2566(8) 0.5967(4) 0.54597(19) 0.0554(12) Uani 1 1 d . . . . .
C9 C 0.3949(8) 0.5625(4) 0.63678(18) 0.0586(13) Uani 1 1 d . . . . .
C8 C 0.5587(8) 0.6141(4) 0.66656(19) 0.0621(13) Uani 1 1 d . . . . .
C6 C 0.5215(8) 0.9063(5) 0.68150(18) 0.0602(13) Uani 1 1 d . . . . .
C12 C 0.4578(8) 0.6370(4) 0.5258(2) 0.0666(14) Uani 1 1 d . . . . .
H12 H 0.565244 0.666454 0.548577 0.080 Uiso 1 1 calc R . . . .
C17 C 0.3500(10) 0.3626(4) 0.6146(2) 0.0641(13) Uani 1 1 d . . . . .
C7 C 0.5870(8) 0.7295(4) 0.67821(17) 0.0619(13) Uani 1 1 d . . . . .
C5 C 0.4123(8) 1.0055(5) 0.6726(2) 0.0717(15) Uani 1 1 d . . . . .
H5 H 0.274179 1.007303 0.654750 0.086 Uiso 1 1 calc R . . . .
C10 C 0.2051(8) 0.6032(4) 0.60388(18) 0.0611(13) Uani 1 1 d . . . . .
H10A H 0.173191 0.678666 0.613147 0.073 Uiso 1 1 calc R . . . .
H10B H 0.069669 0.560431 0.611296 0.073 Uiso 1 1 calc R . . . .
C1 C 0.7298(8) 0.9058(4) 0.70818(19) 0.0633(13) Uani 1 1 d . . . . .
C13 C 0.5037(9) 0.6347(4) 0.4728(2) 0.0751(16) Uani 1 1 d . . . . .
H13 H 0.640483 0.662544 0.460163 0.090 Uiso 1 1 calc R . . . .
C22 C 0.4607(10) 0.3128(4) 0.5742(2) 0.0743(16) Uani 1 1 d . . . . .
H22 H 0.600953 0.339146 0.562913 0.089 Uiso 1 1 calc R . . . .
C16 C 0.1041(9) 0.5520(4) 0.5112(2) 0.0734(16) Uani 1 1 d . . . . .
H16 H -0.031113 0.522206 0.523683 0.088 Uiso 1 1 calc R . . . .
C2 C 0.8288(9) 1.0018(5) 0.7258(2) 0.0793(16) Uani 1 1 d . . . . .
H2 H 0.967764 1.000909 0.743358 0.095 Uiso 1 1 calc R . . . .
C3 C 0.7157(10) 1.0986(5) 0.7167(2) 0.0819(16) Uani 1 1 d . . . . .
H3 H 0.778865 1.163886 0.728629 0.098 Uiso 1 1 calc R . . . .
C14 C 0.3467(11) 0.5912(4) 0.4387(2) 0.0802(16) Uani 1 1 d . . . . .
H14 H 0.375583 0.589409 0.402814 0.096 Uiso 1 1 calc R . . . .
C18 C 0.1414(11) 0.3255(5) 0.6319(2) 0.0812(17) Uani 1 1 d . . . . .
H18 H 0.065690 0.359963 0.659378 0.097 Uiso 1 1 calc R . . . .
C4 C 0.5096(10) 1.1010(5) 0.6902(2) 0.0794(16) Uani 1 1 d . . . . .
H4 H 0.436793 1.167461 0.684396 0.095 Uiso 1 1 calc R . . . .
C15 C 0.1476(11) 0.5505(4) 0.4583(2) 0.0877(18) Uani 1 1 d . . . . .
H15 H 0.039939 0.521404 0.435453 0.105 Uiso 1 1 calc R . . . .
C19 C 0.0485(10) 0.2353(5) 0.6070(3) 0.0912(19) Uani 1 1 d . . . . .
H19 H -0.092194 0.209102 0.618093 0.109 Uiso 1 1 calc R . . . .
C20 C 0.1572(13) 0.1839(5) 0.5669(3) 0.094(2) Uani 1 1 d . . . . .
H20 H 0.092240 0.122905 0.550932 0.113 Uiso 1 1 calc R . . . .
C21 C 0.3632(12) 0.2227(4) 0.5501(2) 0.0900(18) Uani 1 1 d . . . . .
H21 H 0.437972 0.188518 0.522434 0.108 Uiso 1 1 calc R . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
S1 C7 1.746(5) . ?
S1 C1 1.730(5) . ?
N2 N3 1.360(5) . ?
N2 C9 1.359(5) . ?
N2 C17 1.434(6) . ?
N1 C6 1.389(6) . ?
N1 C7 1.293(5) . ?
N3 N4 1.304(5) . ?
N4 C8 1.368(5) . ?
C11 C12 1.380(6) . ?
C11 C10 1.508(6) . ?
C11 C16 1.374(6) . ?
C9 C8 1.378(6) . ?
C9 C10 1.481(6) . ?
C8 C7 1.450(6) . ?
C6 C5 1.390(6) . ?
C6 C1 1.399(6) . ?
C12 C13 1.375(7) . ?
C17 C22 1.360(6) . ?
C17 C18 1.379(7) . ?
C5 C4 1.374(7) . ?
C1 C2 1.385(6) . ?
C13 C14 1.375(7) . ?
C22 C21 1.385(7) . ?
C16 C15 1.370(7) . ?
C2 C3 1.376(7) . ?
C3 C4 1.386(7) . ?
C14 C15 1.365(7) . ?
C18 C19 1.383(7) . ?
C19 C20 1.360(7) . ?
C20 C21 1.368(8) . ?

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 S1 C7 88.8(2) . . ?
N3 N2 C17 119.7(4) . . ?
C9 N2 N3 111.4(4) . . ?
C9 N2 C17 128.9(4) . . ?
C7 N1 C6 109.8(4) . . ?
N4 N3 N2 106.9(4) . . ?
N3 N4 C8 109.3(4) . . ?
C12 C11 C10 121.2(4) . . ?
C16 C11 C12 117.4(5) . . ?
C16 C11 C10 121.4(5) . . ?
N2 C9 C8 103.5(4) . . ?
N2 C9 C10 123.2(5) . . ?
C8 C9 C10 133.1(5) . . ?
N4 C8 C9 108.9(5) . . ?
N4 C8 C7 121.4(5) . . ?
C9 C8 C7 129.6(4) . . ?
N1 C6 C5 125.2(5) . . ?
N1 C6 C1 115.6(5) . . ?
C5 C6 C1 119.2(5) . . ?
C13 C12 C11 121.7(5) . . ?
C22 C17 N2 119.3(5) . . ?
C22 C17 C18 121.3(6) . . ?
C18 C17 N2 119.5(5) . . ?
N1 C7 S1 116.6(4) . . ?
N1 C7 C8 124.2(4) . . ?
C8 C7 S1 119.2(4) . . ?
C4 C5 C6 119.6(5) . . ?
C9 C10 C11 112.6(4) . . ?
C6 C1 S1 109.2(4) . . ?
C2 C1 S1 129.4(4) . . ?
C2 C1 C6 121.4(5) . . ?
C14 C13 C12 119.7(5) . . ?
C17 C22 C21 119.5(6) . . ?
C15 C16 C11 121.2(5) . . ?
C3 C2 C1 118.1(5) . . ?
C2 C3 C4 121.4(6) . . ?
C15 C14 C13 119.0(5) . . ?
C17 C18 C19 117.8(6) . . ?
C5 C4 C3 120.3(6) . . ?
C14 C15 C16 120.9(5) . . ?
C20 C19 C18 121.8(6) . . ?
C19 C20 C21 119.3(6) . . ?
C20 C21 C22 120.2(6) . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.581
_oxdiff_exptl_absorpt_empirical_full_min 0.426
####################################################################### 
# 
# 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_dbr36
_database_code_depnum_ccdc_archive 'CCDC 2384642'
loop_
_audit_author_name
_audit_author_address
'Raghavaiah Pallepogu'
;Central University of Karnataka
India
;
_audit_update_record             
;
2024-09-17 deposited with the CCDC.	2025-01-13 downloaded from the CCDC.
;
_audit_creation_date             2022-07-26
_audit_creation_method           
;
Olex2 1.3-ac4
(compiled 2018.12.18 svn.r3554 for Rigaku Oxford Diffraction, GUI svn.r1)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C23 H15 F3 N4 S'
_chemical_formula_sum            'C23 H15 F3 N4 S'
_chemical_formula_weight         436.45
_chemical_absolute_configuration ?
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C H N O S F'
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'
F F 0.0171 0.0103 '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'
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      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   6.3340(2)
_cell_length_b                   12.0464(5)
_cell_length_c                   26.3054(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2007.15(13)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    8781
_cell_measurement_temperature    295.3(5)
_cell_measurement_theta_max      26.7140
_cell_measurement_theta_min      2.2860
_shelx_estimated_absorpt_T_max   0.980
_shelx_estimated_absorpt_T_min   0.960
_exptl_absorpt_coefficient_mu    0.207
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56637
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.35a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.444
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0336
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            14138
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.922
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.235
_diffrn_reflns_theta_min         2.293
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.3(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -24.00  21.00   0.50   18.00    --  -15.60 -94.00   0.00   90
  2  ω    -74.00   1.00   0.50   18.00    --  -15.60 -30.00  90.00  150
  3  ω     24.00  87.00   0.50   18.00    --   16.22-150.00 148.00  126
  4  ω    -86.00  -3.00   0.50   18.00    --  -15.60 -45.00   0.00  166
  5  ω     54.00  85.00   0.50   18.00    --   16.22  45.00 -90.00   62
  6  ω    -95.00  67.00   0.50   18.00    --  -15.60   8.00-125.00  324
  7  ω    -80.00 -18.00   0.50   18.00    --  -15.60 141.00 109.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0125828000
_diffrn_orient_matrix_UB_12      0.0098951000
_diffrn_orient_matrix_UB_13      0.0264047000
_diffrn_orient_matrix_UB_21      0.0075020000
_diffrn_orient_matrix_UB_22      0.0579564000
_diffrn_orient_matrix_UB_23      -0.0043599000
_diffrn_orient_matrix_UB_31      -0.1110647000
_diffrn_orient_matrix_UB_32      0.0028466000
_diffrn_orient_matrix_UB_33      -0.0032710000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_reflns_Friedel_coverage         0.676
_reflns_Friedel_fraction_full    0.958
_reflns_Friedel_fraction_max     0.881
_reflns_number_gt                3350
_reflns_number_total             4137
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.35a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.584
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details 
;
 Flack x determined using 1159 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         4137
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0754
_refine_ls_R_factor_gt           0.0642
_refine_ls_restrained_S_all      1.099
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1100P)²+0.5225P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1845
_refine_ls_wR_factor_ref         0.1950
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C15(H15), C14(H14), C22(H22), C18(H18), C7(H7), C5(H5),
 C8(H8), C6(H6), C20(H20), C21(H21), C19(H19)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
S1 S 0.8600(2) 0.12919(13) 0.70372(6) 0.0671(4) Uani 1 1 d . . . . .
N1 N 0.4820(6) 0.4519(3) 0.64391(14) 0.0508(9) Uani 1 1 d . . . . .
N4 N 0.4788(7) 0.0998(3) 0.67041(15) 0.0558(10) Uani 1 1 d . . . . .
N2 N 0.6724(7) 0.4662(4) 0.66731(17) 0.0589(10) Uani 1 1 d . . . . .
N3 N 0.7392(6) 0.3678(4) 0.67969(16) 0.0574(10) Uani 1 1 d . . . . .
C1 C 0.4292(7) 0.3436(4) 0.64030(16) 0.0482(10) Uani 1 1 d . . . . .
C10 C 0.3681(8) 0.5477(4) 0.62747(17) 0.0491(10) Uani 1 1 d . . . . .
C4 C 0.5519(8) -0.0027(4) 0.68803(16) 0.0529(11) Uani 1 1 d . . . . .
C17 C 0.1956(7) 0.3486(4) 0.56259(18) 0.0508(11) Uani 1 1 d . . . . .
C2 C 0.5960(7) 0.2909(4) 0.66411(16) 0.0493(10) Uani 1 1 d . . . . .
C3 C 0.6233(7) 0.1738(4) 0.67670(16) 0.0493(10) Uani 1 1 d . . . . .
C11 C 0.1679(8) 0.5667(4) 0.64728(19) 0.0559(11) Uani 1 1 d . . . . .
H11 H 0.110435 0.518728 0.671266 0.067 Uiso 1 1 calc R . . . .
F3 F 0.0768(11) 0.8610(5) 0.5324(2) 0.150(2) Uani 1 1 d . . . . .
C9 C 0.7530(9) -0.0013(5) 0.70819(18) 0.0566(11) Uani 1 1 d . . . . .
C12 C 0.0566(8) 0.6577(4) 0.63075(19) 0.0573(12) Uani 1 1 d . . . . .
H12 H -0.077064 0.672136 0.643838 0.069 Uiso 1 1 calc R . . . .
C16 C 0.2358(8) 0.3010(4) 0.61516(19) 0.0584(12) Uani 1 1 d . . . . .
H16A H 0.115253 0.317492 0.636607 0.070 Uiso 1 1 calc R . . . .
H16B H 0.246466 0.220871 0.612411 0.070 Uiso 1 1 calc R . . . .
C13 C 0.1430(9) 0.7282(4) 0.59459(19) 0.0559(11) Uani 1 1 d . . . . .
C15 C 0.4563(8) 0.6181(4) 0.5923(2) 0.0608(12) Uani 1 1 d . . . . .
H15 H 0.590488 0.604217 0.579401 0.073 Uiso 1 1 calc R . . . .
C23 C 0.0201(10) 0.8234(5) 0.5761(2) 0.0690(14) Uani 1 1 d . . . . .
C14 C 0.3445(9) 0.7090(5) 0.5764(2) 0.0628(13) Uani 1 1 d . . . . .
H14 H 0.404397 0.758126 0.553211 0.075 Uiso 1 1 calc R . . . .
C22 C 0.3500(10) 0.3443(4) 0.5250(2) 0.0657(13) Uani 1 1 d . . . . .
H22 H 0.480176 0.311879 0.531876 0.079 Uiso 1 1 calc R . . . .
C18 C 0.0061(9) 0.3971(5) 0.5514(2) 0.0662(13) Uani 1 1 d . . . . .
H18 H -0.098312 0.400805 0.576223 0.079 Uiso 1 1 calc R . . . .
C7 C 0.7239(11) -0.1936(5) 0.7274(2) 0.0738(16) Uani 1 1 d . . . . .
H7 H 0.780465 -0.258874 0.740454 0.089 Uiso 1 1 calc R . . . .
C5 C 0.4350(10) -0.0997(5) 0.6873(2) 0.0659(14) Uani 1 1 d . . . . .
H5 H 0.300224 -0.100734 0.673290 0.079 Uiso 1 1 calc R . . . .
C8 C 0.8427(10) -0.0991(5) 0.7283(2) 0.0695(15) Uani 1 1 d . . . . .
H8 H 0.978454 -0.099096 0.741793 0.083 Uiso 1 1 calc R . . . .
C6 C 0.5217(11) -0.1949(5) 0.7076(2) 0.0697(15) Uani 1 1 d . . . . .
H6 H 0.443688 -0.260257 0.708066 0.084 Uiso 1 1 calc R . . . .
C20 C 0.1174(15) 0.4372(5) 0.4670(2) 0.090(2) Uani 1 1 d . . . . .
H20 H 0.090662 0.467681 0.435187 0.108 Uiso 1 1 calc R . . . .
C21 C 0.3094(12) 0.3885(5) 0.4769(2) 0.0813(18) Uani 1 1 d . . . . .
H21 H 0.411918 0.384990 0.451641 0.098 Uiso 1 1 calc R . . . .
C19 C -0.0324(12) 0.4410(6) 0.5035(2) 0.0813(18) Uani 1 1 d . . . . .
H19 H -0.162544 0.473228 0.496523 0.098 Uiso 1 1 calc R . . . .
F2 F 0.0168(18) 0.9050(5) 0.6029(2) 0.259(6) Uani 1 1 d . . . . .
F1 F -0.1697(10) 0.8012(7) 0.5652(5) 0.246(6) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
S1 C3 1.744(5) . ?
S1 C9 1.716(6) . ?
N1 N2 1.365(6) . ?
N1 C1 1.351(6) . ?
N1 C10 1.427(6) . ?
N4 C4 1.398(6) . ?
N4 C3 1.288(6) . ?
N2 N3 1.299(6) . ?
N3 C2 1.361(6) . ?
C1 C2 1.382(6) . ?
C1 C16 1.484(6) . ?
C10 C11 1.390(7) . ?
C10 C15 1.375(7) . ?
C4 C9 1.380(7) . ?
C4 C5 1.383(8) . ?
C17 C16 1.519(6) . ?
C17 C22 1.392(7) . ?
C17 C18 1.367(7) . ?
C2 C3 1.459(7) . ?
C11 H11 0.9300 . ?
C11 C12 1.375(7) . ?
F3 C23 1.286(7) . ?
C9 C8 1.410(8) . ?
C12 H12 0.9300 . ?
C12 C13 1.387(7) . ?
C16 H16A 0.9700 . ?
C16 H16B 0.9700 . ?
C13 C23 1.469(8) . ?
C13 C14 1.383(8) . ?
C15 H15 0.9300 . ?
C15 C14 1.370(7) . ?
C23 F2 1.210(7) . ?
C23 F1 1.264(9) . ?
C14 H14 0.9300 . ?
C22 H22 0.9300 . ?
C22 C21 1.396(8) . ?
C18 H18 0.9300 . ?
C18 C19 1.387(8) . ?
C7 H7 0.9300 . ?
C7 C8 1.365(9) . ?
C7 C6 1.382(9) . ?
C5 H5 0.9300 . ?
C5 C6 1.379(8) . ?
C8 H8 0.9300 . ?
C6 H6 0.9300 . ?
C20 H20 0.9300 . ?
C20 C21 1.375(11) . ?
C20 C19 1.351(10) . ?
C21 H21 0.9300 . ?
C19 H19 0.9300 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C9 S1 C3 88.3(2) . . ?
N2 N1 C10 118.8(4) . . ?
C1 N1 N2 111.8(4) . . ?
C1 N1 C10 129.4(4) . . ?
C3 N4 C4 109.5(4) . . ?
N3 N2 N1 106.6(4) . . ?
N2 N3 C2 109.2(4) . . ?
N1 C1 C2 102.9(4) . . ?
N1 C1 C16 124.7(4) . . ?
C2 C1 C16 132.4(4) . . ?
C11 C10 N1 118.7(4) . . ?
C15 C10 N1 119.8(4) . . ?
C15 C10 C11 121.4(5) . . ?
C9 C4 N4 115.0(5) . . ?
C9 C4 C5 120.6(5) . . ?
C5 C4 N4 124.3(5) . . ?
C22 C17 C16 121.0(4) . . ?
C18 C17 C16 120.3(5) . . ?
C18 C17 C22 118.7(5) . . ?
N3 C2 C1 109.5(4) . . ?
N3 C2 C3 120.7(4) . . ?
C1 C2 C3 129.6(4) . . ?
N4 C3 S1 116.7(4) . . ?
N4 C3 C2 123.7(4) . . ?
C2 C3 S1 119.5(3) . . ?
C10 C11 H11 120.6 . . ?
C12 C11 C10 118.8(4) . . ?
C12 C11 H11 120.6 . . ?
C4 C9 S1 110.5(4) . . ?
C4 C9 C8 120.4(5) . . ?
C8 C9 S1 129.1(4) . . ?
C11 C12 H12 119.9 . . ?
C11 C12 C13 120.2(5) . . ?
C13 C12 H12 119.9 . . ?
C1 C16 C17 114.4(4) . . ?
C1 C16 H16A 108.7 . . ?
C1 C16 H16B 108.7 . . ?
C17 C16 H16A 108.7 . . ?
C17 C16 H16B 108.7 . . ?
H16A C16 H16B 107.6 . . ?
C12 C13 C23 119.7(5) . . ?
C14 C13 C12 120.0(5) . . ?
C14 C13 C23 120.3(5) . . ?
C10 C15 H15 120.4 . . ?
C14 C15 C10 119.3(5) . . ?
C14 C15 H15 120.4 . . ?
F3 C23 C13 115.1(5) . . ?
F2 C23 F3 103.9(7) . . ?
F2 C23 C13 116.7(6) . . ?
F2 C23 F1 106.7(8) . . ?
F1 C23 F3 98.0(7) . . ?
F1 C23 C13 114.4(6) . . ?
C13 C14 H14 119.8 . . ?
C15 C14 C13 120.3(5) . . ?
C15 C14 H14 119.8 . . ?
C17 C22 H22 120.0 . . ?
C17 C22 C21 120.0(6) . . ?
C21 C22 H22 120.0 . . ?
C17 C18 H18 119.6 . . ?
C17 C18 C19 120.8(6) . . ?
C19 C18 H18 119.6 . . ?
C8 C7 H7 119.1 . . ?
C8 C7 C6 121.8(5) . . ?
C6 C7 H7 119.1 . . ?
C4 C5 H5 120.5 . . ?
C6 C5 C4 118.9(5) . . ?
C6 C5 H5 120.5 . . ?
C9 C8 H8 121.1 . . ?
C7 C8 C9 117.9(6) . . ?
C7 C8 H8 121.1 . . ?
C7 C6 H6 119.8 . . ?
C5 C6 C7 120.4(6) . . ?
C5 C6 H6 119.8 . . ?
C21 C20 H20 120.0 . . ?
C19 C20 H20 120.0 . . ?
C19 C20 C21 120.1(6) . . ?
C22 C21 H21 120.1 . . ?
C20 C21 C22 119.8(6) . . ?
C20 C21 H21 120.1 . . ?
C18 C19 H19 119.7 . . ?
C20 C19 C18 120.6(6) . . ?
C20 C19 H19 119.7 . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.602
_oxdiff_exptl_absorpt_empirical_full_min 0.473
