# Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.
# This journal is © the Owner Societies 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_mrk_kcb_13_autored
_database_code_depnum_ccdc_archive 'CCDC 2294221'
loop_
_audit_author_name
_audit_author_address
'Kanhu Charan Behera'
;IIT Bombay
India
;
_audit_update_record             
;
2023-09-11 deposited with the CCDC.	2024-01-25 downloaded from the CCDC.
;
_audit_creation_date             2023-09-11
_audit_creation_method           
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        'a-benzethizoyl-3-pyrrolyl BODIPY'
_chemical_formula_moiety         'C27 H19 B F2 N4 S'
_chemical_formula_sum            'C27 H19 B F2 N4 S'
_chemical_formula_weight         480.33
_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'
B B 0.0013 0.0007 '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      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   19.5653(3)
_cell_length_b                   16.6631(2)
_cell_length_c                   14.1015(2)
_cell_angle_alpha                90
_cell_angle_beta                 107.245(2)
_cell_angle_gamma                90
_cell_volume                     4390.68(12)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    27586
_cell_measurement_temperature    106(8)
_cell_measurement_theta_max      33.9000
_cell_measurement_theta_min      1.7320
_shelx_estimated_absorpt_T_max   0.998
_shelx_estimated_absorpt_T_min   0.978
_exptl_absorpt_coefficient_mu    0.190
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60614
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            olive
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.453
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             1984
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.011
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1591
_diffrn_reflns_av_unetI/netI     0.0682
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            54489
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.637
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      106(8)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  φ    154.25 334.25   1.00    1.00 -25.75   0.00  73.76    --   180
  2  ω    -96.04  19.96   1.00   10.00    --   -5.07 -59.25-123.92  116
  3  ω    -96.04  19.96   1.00   10.00    --   -5.07 -59.25 -51.92  116
  4  ω    -62.98   0.02   1.00   10.00    --  -16.86  94.56  73.16   63
  5  φ    -65.73 118.27   1.00   10.00  11.39  -5.07 -31.50    --   184
  6  ω    -62.98   0.02   1.00   10.00    --  -16.86  94.56   1.16   63
  7  φ   -214.27  33.73   1.00   10.00  85.79  -5.07  31.50    --   248
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type  
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0303714000
_diffrn_orient_matrix_UB_12      -0.0254171000
_diffrn_orient_matrix_UB_13      0.0152230000
_diffrn_orient_matrix_UB_21      -0.0011217000
_diffrn_orient_matrix_UB_22      -0.0055510000
_diffrn_orient_matrix_UB_23      -0.0503115000
_diffrn_orient_matrix_UB_31      0.0227321000
_diffrn_orient_matrix_UB_32      0.0337003000
_diffrn_orient_matrix_UB_33      0.0032198000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3628
_reflns_number_total             3845
_reflns_odcompleteness_completeness 78.35
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     35.93
_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 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.312
_refine_diff_density_rms         0.073
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         3845
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0382
_refine_ls_R_factor_gt           0.0348
_refine_ls_restrained_S_all      1.070
_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)+3.5088P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0940
_refine_ls_wR_factor_ref         0.0962
_refine_special_details          ?
_olex2_refinement_description    
;
1.a Aromatic/amide H refined with riding coordinates:
 N3(H004), C22(H008), C23(H00A), C26(H00E), C25(H00F), C3(H00H), C8(H00K),
 C1(H00M), C19(H00N), C11(H00O), C7(H00Q), C12(H00R), C2(H00T), C16(H00V),
 C18(H00W), C17(H00X)
1.b Idealised Me refined as rotating group:
 C27(H00B,H00C,H00D)
;
_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 0.74424(2) 0.71232(2) 0.61504(3) 0.01950(13) Uani 1 1 d . . . . .
F1 F 0.62975(5) 0.36507(5) 0.57122(6) 0.0258(2) Uani 1 1 d . . . . .
F2 F 0.66917(4) 0.36033(5) 0.43590(7) 0.0257(2) Uani 1 1 d . . . . .
N1 N 0.60930(6) 0.24410(7) 0.47240(9) 0.0148(3) Uani 1 1 d . . . . .
N2 N 0.54140(6) 0.36880(7) 0.41029(8) 0.0127(3) Uani 1 1 d . . . . .
N3 N 0.63375(6) 0.51899(7) 0.48326(9) 0.0141(3) Uani 1 1 d . . . . .
H004 H 0.659201 0.476566 0.509364 0.017 Uiso 1 1 calc R . . . .
N4 N 0.77177(6) 0.55942(7) 0.61266(9) 0.0171(3) Uani 1 1 d . . . . .
C1 C 0.66415(8) 0.19211(9) 0.50762(11) 0.0188(3) Uani 1 1 d . . . . .
H00M H 0.712276 0.206963 0.540205 0.023 Uiso 1 1 calc R . . . .
C2 C 0.63951(8) 0.11385(9) 0.48897(12) 0.0223(3) Uani 1 1 d . . . . .
H00T H 0.667458 0.066399 0.505272 0.027 Uiso 1 1 calc R . . . .
C3 C 0.56636(8) 0.11788(9) 0.44202(11) 0.0197(3) Uani 1 1 d . . . . .
H00H H 0.534852 0.073693 0.420750 0.024 Uiso 1 1 calc R . . . .
C4 C 0.54770(7) 0.19949(9) 0.43189(10) 0.0154(3) Uani 1 1 d . . . . .
C5 C 0.48222(7) 0.23838(8) 0.38445(10) 0.0143(3) Uani 1 1 d . . . . .
C6 C 0.48040(7) 0.32103(8) 0.37113(10) 0.0136(3) Uani 1 1 d . . . . .
C7 C 0.42263(7) 0.37280(8) 0.32394(10) 0.0157(3) Uani 1 1 d . . . . .
H00Q H 0.374857 0.356831 0.291061 0.019 Uiso 1 1 calc R . . . .
C8 C 0.44808(7) 0.44959(9) 0.33430(10) 0.0161(3) Uani 1 1 d . . . . .
H00K H 0.421325 0.496561 0.309115 0.019 Uiso 1 1 calc R . . . .
C9 C 0.52180(7) 0.44671(8) 0.38954(10) 0.0134(3) Uani 1 1 d . . . . .
C10 C 0.56544(7) 0.51690(8) 0.41963(10) 0.0148(3) Uani 1 1 d . . . . .
C11 C 0.54528(8) 0.59641(9) 0.39441(11) 0.0180(3) Uani 1 1 d . . . . .
H00O H 0.500735 0.613714 0.350866 0.022 Uiso 1 1 calc R . . . .
C12 C 0.60220(8) 0.64602(8) 0.44453(11) 0.0185(3) Uani 1 1 d . . . . .
H00R H 0.603539 0.702913 0.441212 0.022 Uiso 1 1 calc R . . . .
C13 C 0.65636(7) 0.59640(8) 0.50004(10) 0.0155(3) Uani 1 1 d . . . . .
C14 C 0.72450(7) 0.61417(8) 0.57197(10) 0.0155(3) Uani 1 1 d . . . . .
C15 C 0.82399(8) 0.67784(9) 0.69468(11) 0.0181(3) Uani 1 1 d . . . . .
C16 C 0.87764(8) 0.72141(9) 0.76321(11) 0.0223(3) Uani 1 1 d . . . . .
H00V H 0.873734 0.777797 0.770138 0.027 Uiso 1 1 calc R . . . .
C17 C 0.93602(8) 0.67990(10) 0.82001(11) 0.0245(4) Uani 1 1 d . . . . .
H00X H 0.973309 0.708156 0.866688 0.029 Uiso 1 1 calc R . . . .
C18 C 0.94176(8) 0.59660(10) 0.81053(12) 0.0245(4) Uani 1 1 d . . . . .
H00W H 0.982487 0.569382 0.851601 0.029 Uiso 1 1 calc R . . . .
C19 C 0.88921(8) 0.55334(9) 0.74247(11) 0.0219(3) Uani 1 1 d . . . . .
H00N H 0.893700 0.496983 0.736089 0.026 Uiso 1 1 calc R . . . .
C20 C 0.82941(7) 0.59424(9) 0.68331(11) 0.0169(3) Uani 1 1 d . . . . .
C21 C 0.41555(7) 0.18972(8) 0.35562(10) 0.0148(3) Uani 1 1 d . . . . .
C22 C 0.36742(8) 0.19001(9) 0.26011(11) 0.0168(3) Uani 1 1 d . . . . .
H008 H 0.377182 0.221703 0.209643 0.020 Uiso 1 1 calc R . . . .
C23 C 0.30523(7) 0.14418(8) 0.23835(11) 0.0171(3) Uani 1 1 d . . . . .
H00A H 0.273413 0.144410 0.172721 0.021 Uiso 1 1 calc R . . . .
C24 C 0.28869(7) 0.09791(8) 0.31103(11) 0.0163(3) Uani 1 1 d . . . . .
C25 C 0.33678(7) 0.09827(8) 0.40643(11) 0.0164(3) Uani 1 1 d . . . . .
H00F H 0.326368 0.067678 0.457294 0.020 Uiso 1 1 calc R . . . .
C26 C 0.39951(7) 0.14250(8) 0.42830(11) 0.0160(3) Uani 1 1 d . . . . .
H00E H 0.432018 0.140753 0.493422 0.019 Uiso 1 1 calc R . . . .
C27 C 0.22112(8) 0.04884(9) 0.28809(11) 0.0208(3) Uani 1 1 d . . . . .
H00B H 0.184792 0.078201 0.309312 0.031 Uiso 1 1 calc GR . . . .
H00C H 0.231169 -0.002436 0.323552 0.031 Uiso 1 1 calc GR . . . .
H00D H 0.203436 0.038809 0.216471 0.031 Uiso 1 1 calc GR . . . .
B1 B 0.61450(8) 0.33566(10) 0.47415(12) 0.0165(3) 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 C14 1.7475(14) . ?
S1 C15 1.7283(15) . ?
F1 B1 1.4003(19) . ?
F2 B1 1.3949(18) . ?
N1 C1 1.3538(18) . ?
N1 C4 1.3868(18) . ?
N1 B1 1.529(2) . ?
N2 C6 1.4044(17) . ?
N2 C9 1.3607(18) . ?
N2 B1 1.5485(18) . ?
N3 C10 1.3717(18) . ?
N3 C13 1.3613(18) . ?
N4 C14 1.3048(18) . ?
N4 C20 1.3910(19) . ?
C1 C2 1.388(2) . ?
C3 C2 1.389(2) . ?
C4 C3 1.404(2) . ?
C4 C5 1.4145(19) . ?
C5 C6 1.389(2) . ?
C6 C7 1.4207(19) . ?
C8 C7 1.365(2) . ?
C9 C8 1.4226(19) . ?
C9 C10 1.436(2) . ?
C10 C11 1.398(2) . ?
C11 C12 1.399(2) . ?
C13 C12 1.388(2) . ?
C13 C14 1.446(2) . ?
C16 C15 1.401(2) . ?
C16 C17 1.372(2) . ?
C18 C17 1.402(2) . ?
C19 C18 1.383(2) . ?
C19 C20 1.397(2) . ?
C20 C15 1.410(2) . ?
C21 C5 1.4865(19) . ?
C22 C21 1.396(2) . ?
C22 C23 1.392(2) . ?
C24 C23 1.395(2) . ?
C24 C25 1.395(2) . ?
C24 C27 1.5057(19) . ?
C26 C21 1.400(2) . ?
C26 C25 1.386(2) . ?

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
C15 S1 C14 88.78(7) . . ?
C1 N1 C4 107.80(12) . . ?
C1 N1 B1 126.22(12) . . ?
C4 N1 B1 125.96(11) . . ?
C6 N2 B1 123.86(11) . . ?
C9 N2 C6 107.69(11) . . ?
C9 N2 B1 128.18(12) . . ?
C13 N3 C10 109.94(12) . . ?
C14 N4 C20 109.98(12) . . ?
N1 C1 C2 109.79(13) . . ?
C1 C2 C3 107.20(13) . . ?
C2 C3 C4 107.18(13) . . ?
N1 C4 C3 108.01(12) . . ?
N1 C4 C5 120.26(13) . . ?
C3 C4 C5 131.57(13) . . ?
C4 C5 C21 118.54(12) . . ?
C6 C5 C4 120.11(12) . . ?
C6 C5 C21 121.23(12) . . ?
N2 C6 C7 107.78(12) . . ?
C5 C6 N2 121.61(12) . . ?
C5 C6 C7 130.57(13) . . ?
C8 C7 C6 107.75(12) . . ?
C7 C8 C9 107.79(12) . . ?
N2 C9 C8 108.98(12) . . ?
N2 C9 C10 127.49(12) . . ?
C8 C9 C10 123.50(12) . . ?
N3 C10 C9 126.34(12) . . ?
N3 C10 C11 106.81(12) . . ?
C11 C10 C9 126.76(13) . . ?
C10 C11 C12 108.01(13) . . ?
C13 C12 C11 107.05(13) . . ?
N3 C13 C12 108.18(12) . . ?
N3 C13 C14 120.02(13) . . ?
C12 C13 C14 131.62(13) . . ?
N4 C14 S1 116.53(11) . . ?
N4 C14 C13 123.44(13) . . ?
C13 C14 S1 119.88(11) . . ?
C16 C15 S1 128.58(12) . . ?
C16 C15 C20 121.63(14) . . ?
C20 C15 S1 109.78(11) . . ?
C17 C16 C15 117.73(14) . . ?
C16 C17 C18 121.32(14) . . ?
C19 C18 C17 121.20(15) . . ?
C18 C19 C20 118.62(14) . . ?
N4 C20 C15 114.92(13) . . ?
N4 C20 C19 125.59(13) . . ?
C19 C20 C15 119.48(13) . . ?
C22 C21 C5 123.25(13) . . ?
C22 C21 C26 118.35(13) . . ?
C26 C21 C5 118.39(12) . . ?
C23 C22 C21 120.43(13) . . ?
C22 C23 C24 121.29(13) . . ?
C23 C24 C25 117.98(13) . . ?
C23 C24 C27 121.49(13) . . ?
C25 C24 C27 120.53(13) . . ?
C26 C25 C24 121.12(13) . . ?
C25 C26 C21 120.81(13) . . ?
F1 B1 N1 111.04(12) . . ?
F1 B1 N2 109.63(12) . . ?
F2 B1 F1 108.01(12) . . ?
F2 B1 N1 110.05(12) . . ?
F2 B1 N2 110.61(12) . . ?
N1 B1 N2 107.51(11) . . ?

_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.184
_oxdiff_exptl_absorpt_empirical_full_min 0.497
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_preparation       Luminescent
