# Electronic Supplementary Material (ESI) for Green Chemistry.
# This journal is © The Royal Society of Chemistry 2023

####################################################################### 
# 
# 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_3ak
_database_code_depnum_ccdc_archive 'CCDC 2240094'
loop_
_audit_author_name
_audit_author_address
'Jas Ward'
;University of Jyvaskyla
Finland
;
_audit_update_record             
;
2023-02-06 deposited with the CCDC.	2023-03-21 downloaded from the CCDC.
;
_audit_creation_date             2023-02-06
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelxl_version_number           2014/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C14 H12 Cl N3 O S'
_chemical_formula_sum            'C14 H12 Cl N3 O S'
_chemical_formula_weight         305.78
_chemical_absolute_configuration ad
_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 0.0181 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'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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           4
_space_group_name_H-M_alt        'P 1 21 1'
_space_group_name_Hall           'P 2yb'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z'

_cell_length_a                   10.7651(5)
_cell_length_b                   4.8762(2)
_cell_length_c                   13.0778(5)
_cell_angle_alpha                90
_cell_angle_beta                 106.910(5)
_cell_angle_gamma                90
_cell_volume                     656.81(5)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    1480
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      75.6750
_cell_measurement_theta_min      4.2440
_shelx_estimated_absorpt_T_max   0.942
_shelx_estimated_absorpt_T_min   0.469
_exptl_absorpt_coefficient_mu    4.050
_exptl_absorpt_correction_T_max  0.939
_exptl_absorpt_correction_T_min  0.604
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             316
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
5 0 4 0.0137
-5 0 -4 0.0017
1 3 0 0.1069
-1 -3 0 0.1069
5 0 -8 0.0213
-5 0 8 0.0213
4 -1 -7 0.0558
-4 1 7 0.0523

_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.015
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
4.9378 -0.2099 3.9753 -0.0784 0.9969 -0.0090
-4.9378 0.2099 -3.9753 0.0784 -0.9969 0.0090
1.0432 3.1157 0.3583 0.9782 0.1813 0.1009
-1.0432 -3.1157 -0.3583 -0.9782 -0.1813 -0.1009
4.9023 0.1608 -7.5107 -0.0091 -0.0006 1.0000
-4.9023 -0.1608 7.5107 0.0091 0.0006 -1.0000
3.9959 -0.9999 -6.9943 -0.3678 -0.0804 0.8696
-3.9959 0.9999 6.9943 0.3678 0.0804 -0.8696

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_av_unetI/netI     0.0539
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            2727
_diffrn_reflns_point_group_measured_fraction_full 0.770
_diffrn_reflns_point_group_measured_fraction_max 0.745
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.346
_diffrn_reflns_theta_min         3.532
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1947
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω   -112.00 -74.00   1.00    2.00    --  -42.17-143.00 -26.00   38
  2  ω   -116.00 -18.00   1.00    2.00    --  -42.17 -37.00-150.00   98
  3  ω     37.00  90.00   1.00    2.00    --   42.17-125.00  60.00   53
  4  ω    -20.00   8.00   1.00    2.00    --   42.17 -77.00-180.00   28
  5  ω     50.00  75.00   1.00    2.00    --   42.17 -77.00-180.00   25
  6  ω     35.00 107.00   1.00    5.00    --  112.00 -94.00 120.00   72
  7  ω     86.00 171.00   1.00    5.00    --  112.00  45.00-120.00   85
  8  ω     63.00 137.00   1.00    5.00    --  112.00 -61.00 150.00   74
  9  ω     70.00 109.00   1.00    5.00    --  112.00-111.00 -90.00   39
 10  ω     85.00 129.00   1.00    5.00    --  112.00  30.00  30.00   44
 11  ω     39.00  91.00   1.00    5.00    --  112.00 -45.00 120.00   52
 12  ω    105.00 177.00   1.00    5.00    --  112.00 111.00-180.00   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0058186000
_diffrn_orient_matrix_UB_12      0.3154424000
_diffrn_orient_matrix_UB_13      0.0041693000
_diffrn_orient_matrix_UB_21      0.1323648000
_diffrn_orient_matrix_UB_22      0.0039142000
_diffrn_orient_matrix_UB_23      0.0865646000
_diffrn_orient_matrix_UB_31      0.0693917000
_diffrn_orient_matrix_UB_32      0.0192185000
_diffrn_orient_matrix_UB_33      -0.0874342000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_reflns_Friedel_coverage         0.344
_reflns_Friedel_fraction_full    0.478
_reflns_Friedel_fraction_max     0.434
_reflns_number_gt                1877
_reflns_number_total             2001
_reflns_odcompleteness_completeness 98.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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         0.461
_refine_diff_density_min         -0.337
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details 
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     185
_refine_ls_number_reflns         2001
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0431
_refine_ls_restrained_S_all      1.028
_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)+(0.0648P)²+0.1921P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1078
_refine_ls_wR_factor_ref         0.1119
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C15(H15), C16(H16), C18(H18), C19(H19)
2.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_atom_sites_solution_hydrogens   mixed
_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 0.15861(9) 0.6897(2) 0.18839(7) 0.0175(2) Uani 1 1 d . . . . .
N2 N 0.2857(4) 0.5221(9) 0.2306(3) 0.0216(8) Uani 1 1 d . . . . .
C3 C 0.3605(4) 0.5304(10) 0.3346(3) 0.0185(8) Uani 1 1 d . . . . .
N4 N 0.3457(3) 0.6784(10) 0.4137(3) 0.0199(7) Uani 1 1 d . . . . .
C5 C 0.2370(4) 0.8424(10) 0.3947(3) 0.0182(9) Uani 1 1 d . . . . .
C6 C 0.2171(4) 0.9967(11) 0.4802(3) 0.0222(9) Uani 1 1 d . . . . .
H6 H 0.2782 0.9822 0.5489 0.027 Uiso 1 1 calc R . . . .
C7 C 0.1118(4) 1.1671(12) 0.4666(3) 0.0230(9) Uani 1 1 d . . . . .
H7 H 0.1026 1.2698 0.5257 0.028 Uiso 1 1 calc R . . . .
C8 C 0.0173(4) 1.1926(13) 0.3667(3) 0.0251(9) Uani 1 1 d . . . . .
H8 H -0.0553 1.3104 0.3582 0.030 Uiso 1 1 calc R . . . .
C9 C 0.0322(4) 1.0441(11) 0.2824(3) 0.0214(9) Uani 1 1 d . . . . .
H9 H -0.0312 1.0561 0.2146 0.026 Uiso 1 1 calc R . . . .
C10 C 0.1397(4) 0.8757(9) 0.2955(3) 0.0173(9) Uani 1 1 d . . . . .
O11 O 0.0454(3) 0.5316(8) 0.1338(2) 0.0233(7) Uani 1 1 d . . . . .
C12 C 0.1854(5) 0.9227(10) 0.0947(3) 0.0218(9) Uani 1 1 d . . . . .
H12A H 0.2612 1.0364 0.1287 0.033 Uiso 1 1 calc GR . . . .
H12B H 0.1089 1.0401 0.0682 0.033 Uiso 1 1 calc GR . . . .
H12C H 0.2010 0.8216 0.0348 0.033 Uiso 1 1 calc GR . . . .
N13 N 0.4649(4) 0.3567(9) 0.3579(3) 0.0188(8) Uani 1 1 d . . . . .
H13 H 0.506(5) 0.335(15) 0.423(4) 0.023 Uiso 1 1 d R . . . .
C14 C 0.5225(4) 0.2244(10) 0.2872(3) 0.0180(9) Uani 1 1 d . . . . .
C15 C 0.5079(4) 0.3141(12) 0.1820(3) 0.0211(9) Uani 1 1 d . . . . .
H15 H 0.4527 0.4649 0.1538 0.025 Uiso 1 1 calc R . . . .
C16 C 0.5739(4) 0.1826(12) 0.1198(3) 0.0228(9) Uani 1 1 d . . . . .
H16 H 0.5620 0.2404 0.0482 0.027 Uiso 1 1 calc R . . . .
C17 C 0.6566(4) -0.0317(11) 0.1611(3) 0.0197(9) Uani 1 1 d . . . . .
C18 C 0.6735(4) -0.1215(11) 0.2646(3) 0.0221(9) Uani 1 1 d . . . . .
H18 H 0.7310 -0.2690 0.2926 0.026 Uiso 1 1 calc R . . . .
C19 C 0.6061(4) 0.0048(11) 0.3273(3) 0.0219(9) Uani 1 1 d . . . . .
H19 H 0.6168 -0.0584 0.3981 0.026 Uiso 1 1 calc R . . . .
Cl20 Cl 0.74078(10) -0.1924(3) 0.08245(8) 0.0274(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 N2 1.551(4) . ?
S1 C10 1.730(4) . ?
S1 O11 1.443(3) . ?
S1 C12 1.755(4) . ?
N2 C3 1.365(5) . ?
C3 N4 1.309(6) . ?
C3 N13 1.368(6) . ?
N4 C5 1.379(6) . ?
C5 C6 1.415(6) . ?
C5 C10 1.420(5) . ?
C6 H6 0.9500 . ?
C6 C7 1.374(7) . ?
C7 H7 0.9500 . ?
C7 C8 1.408(6) . ?
C8 H8 0.9500 . ?
C8 C9 1.367(7) . ?
C9 H9 0.9500 . ?
C9 C10 1.389(6) . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
N13 H13 0.84(6) . ?
N13 C14 1.411(6) . ?
C14 C15 1.407(6) . ?
C14 C19 1.399(6) . ?
C15 H15 0.9500 . ?
C15 C16 1.384(7) . ?
C16 H16 0.9500 . ?
C16 C17 1.377(7) . ?
C17 C18 1.384(6) . ?
C17 Cl20 1.742(4) . ?
C18 H18 0.9500 . ?
C18 C19 1.388(6) . ?
C19 H19 0.9500 . ?

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
N2 S1 C10 106.7(2) . . ?
N2 S1 C12 106.4(2) . . ?
C10 S1 C12 107.9(2) . . ?
O11 S1 N2 115.2(2) . . ?
O11 S1 C10 113.6(2) . . ?
O11 S1 C12 106.7(2) . . ?
C3 N2 S1 122.9(3) . . ?
N2 C3 N13 114.3(4) . . ?
N4 C3 N2 129.2(4) . . ?
N4 C3 N13 116.5(4) . . ?
C3 N4 C5 118.0(3) . . ?
N4 C5 C6 118.8(4) . . ?
N4 C5 C10 126.4(4) . . ?
C6 C5 C10 114.8(4) . . ?
C5 C6 H6 119.1 . . ?
C7 C6 C5 121.9(4) . . ?
C7 C6 H6 119.1 . . ?
C6 C7 H7 119.3 . . ?
C6 C7 C8 121.3(4) . . ?
C8 C7 H7 119.3 . . ?
C7 C8 H8 120.7 . . ?
C9 C8 C7 118.6(5) . . ?
C9 C8 H8 120.7 . . ?
C8 C9 H9 119.9 . . ?
C8 C9 C10 120.2(4) . . ?
C10 C9 H9 119.9 . . ?
C5 C10 S1 116.8(3) . . ?
C9 C10 S1 120.0(3) . . ?
C9 C10 C5 123.2(4) . . ?
S1 C12 H12A 109.5 . . ?
S1 C12 H12B 109.5 . . ?
S1 C12 H12C 109.5 . . ?
H12A C12 H12B 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C3 N13 H13 117(4) . . ?
C3 N13 C14 128.7(4) . . ?
C14 N13 H13 114(4) . . ?
C15 C14 N13 123.6(4) . . ?
C19 C14 N13 117.5(4) . . ?
C19 C14 C15 118.8(4) . . ?
C14 C15 H15 120.0 . . ?
C16 C15 C14 120.0(5) . . ?
C16 C15 H15 120.0 . . ?
C15 C16 H16 119.8 . . ?
C17 C16 C15 120.3(4) . . ?
C17 C16 H16 119.8 . . ?
C16 C17 C18 120.6(4) . . ?
C16 C17 Cl20 119.9(3) . . ?
C18 C17 Cl20 119.5(4) . . ?
C17 C18 H18 120.2 . . ?
C17 C18 C19 119.7(4) . . ?
C19 C18 H18 120.2 . . ?
C14 C19 H19 119.7 . . ?
C18 C19 C14 120.5(4) . . ?
C18 C19 H19 119.7 . . ?


_ins_header                      
;
TITL RH-P894-b3_numabs_ana in P2(1) 
REM P2(1) (#4 in standard setting)
CELL 1.54184  10.765143   4.876245  13.077758  90.0000 106.9095  90.0000
ZERR    2.00   0.000494   0.000218   0.000532   0.0000   0.0047   0.0000
LATT -1
SYMM -x, y+1/2,-z 
SFAC C H N O S Cl
UNIT 28.00 24.00 6.00 2.00 2.00 2.00
TREF
HKLF 4
END
;
_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 1.351
_oxdiff_exptl_absorpt_empirical_full_min 0.743
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: dichloromethane/pentane'
