# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 2489734'
loop_
_audit_author_name
_audit_author_address
'Akio Saito'
;Tokyo University of Agriculture and Technology
Japan
;
_audit_update_record             
;
2025-09-19 deposited with the CCDC.	2025-12-09 downloaded from the CCDC.
;
_audit_creation_date             2025-05-16
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        
(Z)-5-Benzylidene-2,3-dihydrobenzo[b]thiepin-4(5H)-one
_chemical_formula_moiety         'C17 H14 O S'
_chemical_formula_sum            'C17 H14 O S'
_chemical_formula_weight         266.34
_chemical_melting_point          390.15
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 '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/n 1'
_space_group_name_Hall           '-P 2yn'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   9.7029(4)
_cell_length_b                   9.0406(4)
_cell_length_c                   16.0497(7)
_cell_angle_alpha                90
_cell_angle_beta                 102.413(7)
_cell_angle_gamma                90
_cell_volume                     1374.97(11)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    18812
_cell_measurement_theta_min      4.67
_cell_measurement_theta_max      68.18
_cell_measurement_temperature    263
_shelx_estimated_absorpt_T_max   0.826
_shelx_estimated_absorpt_T_min   0.790
_exptl_absorpt_coefficient_mu    1.982
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'NUMABS (Rigaku, 1999)'
_exptl_absorpt_correction_T_min  0.272
_exptl_absorpt_correction_T_max  0.452
_exptl_absorpt_special_details   ?
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             560
_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.500
_exptl_crystal_size_mid          0.400
_exptl_crystal_size_min          0.400
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0288
_diffrn_reflns_av_unetI/netI     0.0115
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            23834
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.680
_diffrn_reflns_theta_max         68.116
_diffrn_reflns_theta_min         4.907
_diffrn_ambient_temperature      263
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 10.000
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_source                   'rotating anode'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                2373
_reflns_number_total             2489
_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_data_collection       'RAPID AUTO (Rigaku, 2004)'
_computing_cell_refinement       'RAPID AUTO'
_computing_data_reduction        'RAPID AUTO'
_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         0.418
_refine_diff_density_min         -0.358
_refine_diff_density_rms         0.064
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         2489
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0494
_refine_ls_R_factor_gt           0.0482
_refine_ls_restrained_S_all      1.163
_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)+(0.0705P)²+0.2795P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1220
_refine_ls_wR_factor_ref         0.1231
_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:
 C00I(H00I,H00J), C00J(H00K,H00L)
2.b Aromatic/amide H refined with riding coordinates:
 C005(H005), C007(H007), C00A(H00A), C00B(H00B), C00C(H00C), C00D(H00D),
 C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H)
;
_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
S001 S 0.38148(5) 0.41819(6) 0.33631(3) 0.0603(2) Uani 1 1 d . . . . .
O002 O 0.12251(13) 0.16860(14) 0.40868(8) 0.0562(3) Uani 1 1 d . . . . .
C003 C 0.23400(15) 0.49202(17) 0.46535(9) 0.0385(3) Uani 1 1 d . . . . .
C004 C 0.25533(15) 0.34334(17) 0.50496(9) 0.0400(3) Uani 1 1 d . . . . .
C005 C 0.15684(17) 0.59715(18) 0.49992(10) 0.0442(4) Uani 1 1 d . . . . .
H005 H 0.123553 0.572825 0.548351 0.053 Uiso 1 1 calc R . . . .
C006 C 0.31423(16) 0.18722(18) 0.63897(10) 0.0428(4) Uani 1 1 d . . . . .
C007 C 0.29234(16) 0.32571(18) 0.58971(10) 0.0433(4) Uani 1 1 d . . . . .
H007 H 0.306007 0.412406 0.621620 0.052 Uiso 1 1 calc R . . . .
C008 C 0.28552(16) 0.53298(19) 0.39290(10) 0.0433(4) Uani 1 1 d . . . . .
C009 C 0.23751(17) 0.21409(18) 0.44341(10) 0.0442(4) Uani 1 1 d . . . . .
C00A C 0.23466(19) 0.05934(19) 0.61613(11) 0.0505(4) Uani 1 1 d . . . . .
H00A H 0.164120 0.058972 0.566679 0.061 Uiso 1 1 calc R . . . .
C00B C 0.41688(17) 0.1852(2) 0.71497(10) 0.0505(4) Uani 1 1 d . . . . .
H00B H 0.468501 0.270364 0.732971 0.061 Uiso 1 1 calc R . . . .
C00C C 0.25597(19) 0.6746(2) 0.35818(11) 0.0540(4) Uani 1 1 d . . . . .
H00C H 0.290397 0.701883 0.310620 0.065 Uiso 1 1 calc R . . . .
C00D C 0.12824(18) 0.73638(19) 0.46450(12) 0.0521(4) Uani 1 1 d . . . . .
H00D H 0.076358 0.803973 0.488895 0.063 Uiso 1 1 calc R . . . .
C00E C 0.3643(2) -0.0679(2) 0.73917(12) 0.0552(5) Uani 1 1 d . . . . .
H00E H 0.382230 -0.153410 0.771906 0.066 Uiso 1 1 calc R . . . .
C00F C 0.2588(2) -0.0665(2) 0.66564(11) 0.0545(4) Uani 1 1 d . . . . .
H00F H 0.204287 -0.150604 0.649672 0.065 Uiso 1 1 calc R . . . .
C00G C 0.44227(18) 0.0582(2) 0.76347(11) 0.0568(5) Uani 1 1 d . . . . .
H00G H 0.512659 0.057646 0.812989 0.068 Uiso 1 1 calc R . . . .
C00H C 0.1770(2) 0.7740(2) 0.39306(12) 0.0564(5) Uani 1 1 d . . . . .
H00H H 0.156674 0.866644 0.368288 0.068 Uiso 1 1 calc R . . . .
C00I C 0.46879(18) 0.2839(3) 0.41353(14) 0.0656(6) Uani 1 1 d . . . . .
H00I H 0.550544 0.245217 0.395039 0.079 Uiso 1 1 calc R . . . .
H00J H 0.501912 0.332924 0.467912 0.079 Uiso 1 1 calc R . . . .
C00J C 0.3734(2) 0.1560(2) 0.42565(14) 0.0643(5) Uani 1 1 d . . . . .
H00K H 0.353680 0.095353 0.374603 0.077 Uiso 1 1 calc R . . . .
H00L H 0.420459 0.094761 0.472884 0.077 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
S001 C008 1.7698(17) . ?
S001 C00I 1.810(2) . ?
O002 C009 1.207(2) . ?
C003 C004 1.482(2) . ?
C003 C005 1.397(2) . ?
C003 C008 1.410(2) . ?
C004 C007 1.340(2) . ?
C004 C009 1.516(2) . ?
C005 C00D 1.384(2) . ?
C006 C007 1.472(2) . ?
C006 C00A 1.395(2) . ?
C006 C00B 1.399(2) . ?
C008 C00C 1.401(2) . ?
C009 C00J 1.502(2) . ?
C00A C00F 1.379(2) . ?
C00B C00G 1.379(3) . ?
C00C C00H 1.376(3) . ?
C00D C00H 1.374(3) . ?
C00E C00F 1.386(3) . ?
C00E C00G 1.377(3) . ?
C00I C00J 1.520(3) . ?

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
C008 S001 C00I 105.21(8) . . ?
C005 C003 C004 118.95(14) . . ?
C005 C003 C008 117.66(15) . . ?
C008 C003 C004 123.38(14) . . ?
C003 C004 C009 115.70(12) . . ?
C007 C004 C003 121.71(14) . . ?
C007 C004 C009 122.56(14) . . ?
C00D C005 C003 122.20(16) . . ?
C00A C006 C007 123.80(14) . . ?
C00A C006 C00B 117.93(15) . . ?
C00B C006 C007 118.22(15) . . ?
C004 C007 C006 128.53(14) . . ?
C003 C008 S001 126.01(13) . . ?
C00C C008 S001 114.64(13) . . ?
C00C C008 C003 119.29(15) . . ?
O002 C009 C004 121.88(15) . . ?
O002 C009 C00J 123.70(16) . . ?
C00J C009 C004 114.30(14) . . ?
C00F C00A C006 121.11(16) . . ?
C00G C00B C006 120.66(17) . . ?
C00H C00C C008 121.30(16) . . ?
C00H C00D C005 119.54(17) . . ?
C00G C00E C00F 119.61(17) . . ?
C00A C00F C00E 120.06(18) . . ?
C00E C00G C00B 120.56(16) . . ?
C00D C00H C00C 119.98(17) . . ?
C00J C00I S001 112.93(13) . . ?
C009 C00J C00I 109.98(16) . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: hexane and ethyl acetate'
