# Electronic Supplementary Material (ESI) for New Journal of Chemistry.
# This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2017

####################################################################### 
# 
# 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_pm3f
_database_code_depnum_ccdc_archive 'CCDC 1544403'
_audit_update_record             
;
2017-04-17 deposited with the CCDC.
2017-11-02 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
'1-phenyl-3-methyl-4-(3-fluorobenzal)-5-hydroxypyrazole 4-phenylthiosemicarbazone '
_chemical_name_common            PM3FBP-PTSC
_chemical_melting_point          447.6-448.0
_chemical_formula_moiety         C24H20FN5OS
_chemical_formula_sum            'C3.84 H3.20 F0.16 N0.80 O0.16 S0.16'
_chemical_formula_weight         71.28

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'
F F 0.0171 0.0103 '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'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P2(1)/n

loop_
_symmetry_equiv_pos_as_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                   10.700(2)
_cell_length_b                   14.421(3)
_cell_length_c                   14.701(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 101.754(3)
_cell_angle_gamma                90.00
_cell_volume                     2220.9(7)
_cell_formula_units_Z            25
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    10935
_cell_measurement_theta_min      2
_cell_measurement_theta_max      25

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.296
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.148
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.332
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             928
_exptl_absorpt_coefficient_mu    0.181
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Bruker D2 ADVANCE X-ray diffractometer'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            10935
_diffrn_reflns_av_R_equivalents  0.0517
_diffrn_reflns_av_sigmaI/netI    0.0689
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.16
_diffrn_reflns_theta_max         25.00
_reflns_number_total             3840
_reflns_number_gt                2171
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0934P)²+0.4672P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0037(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3840
_refine_ls_number_parameters     291
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1170
_refine_ls_R_factor_gt           0.0677
_refine_ls_wR_factor_ref         0.2045
_refine_ls_wR_factor_gt          0.1750
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_restrained_S_all      1.084
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 1.1871(4) 0.3067(3) 1.1886(3) 0.0582(12) Uani 1 1 d . . .
H1 H 1.2595 0.3019 1.1631 0.070 Uiso 1 1 calc R . .
C2 C 1.1892(6) 0.2769(3) 1.2783(3) 0.0745(15) Uani 1 1 d . . .
H2 H 1.2641 0.2530 1.3140 0.089 Uiso 1 1 calc R . .
C3 C 1.0814(7) 0.2826(4) 1.3150(3) 0.0918(18) Uani 1 1 d . . .
H3 H 1.0826 0.2607 1.3747 0.110 Uiso 1 1 calc R . .
C4 C 0.9715(6) 0.3206(4) 1.2637(3) 0.0957(19) Uani 1 1 d . . .
H4 H 0.8988 0.3245 1.2889 0.115 Uiso 1 1 calc R . .
C5 C 0.9684(5) 0.3530(3) 1.1747(3) 0.0706(14) Uani 1 1 d . . .
H5 H 0.8949 0.3806 1.1407 0.085 Uiso 1 1 calc R . .
C6 C 1.0746(4) 0.3441(3) 1.1373(3) 0.0467(10) Uani 1 1 d . . .
C7 C 1.1532(4) 0.3981(3) 0.9202(3) 0.0477(10) Uani 1 1 d . . .
C8 C 1.2601(4) 0.4232(4) 0.8733(3) 0.0739(14) Uani 1 1 d . . .
H8A H 1.3215 0.4602 0.9145 0.111 Uiso 1 1 calc R . .
H8B H 1.2270 0.4578 0.8179 0.111 Uiso 1 1 calc R . .
H8C H 1.3004 0.3677 0.8575 0.111 Uiso 1 1 calc R . .
C9 C 1.0239(3) 0.3875(2) 0.8895(2) 0.0406(9) Uani 1 1 d . . .
C10 C 0.9702(4) 0.3715(2) 0.9691(2) 0.0433(10) Uani 1 1 d . . .
C11 C 0.9571(4) 0.3905(2) 0.7917(2) 0.0406(9) Uani 1 1 d . . .
C12 C 1.0245(4) 0.3528(3) 0.7203(2) 0.0454(10) Uani 1 1 d . . .
C13 C 1.0258(4) 0.4013(3) 0.6391(3) 0.0575(12) Uani 1 1 d . . .
H13 H 0.9862 0.4588 0.6283 0.069 Uiso 1 1 calc R . .
C14 C 1.0864(5) 0.3625(4) 0.5756(3) 0.0724(14) Uani 1 1 d . . .
C15 C 1.1432(5) 0.2773(4) 0.5863(3) 0.0726(14) Uani 1 1 d . . .
H15 H 1.1833 0.2530 0.5411 0.087 Uiso 1 1 calc R . .
C16 C 1.1393(4) 0.2290(3) 0.6658(3) 0.0651(12) Uani 1 1 d . . .
H16 H 1.1766 0.1706 0.6748 0.078 Uiso 1 1 calc R . .
C17 C 1.0806(4) 0.2659(3) 0.7325(3) 0.0566(11) Uani 1 1 d . . .
H17 H 1.0785 0.2323 0.7862 0.068 Uiso 1 1 calc R . .
C18 C 0.6560(4) 0.4898(3) 0.7848(3) 0.0450(10) Uani 1 1 d . . .
C19 C 0.5203(4) 0.5439(3) 0.6358(3) 0.0509(11) Uani 1 1 d . . .
C20 C 0.5445(5) 0.5994(3) 0.5654(3) 0.0627(13) Uani 1 1 d . . .
H20 H 0.6281 0.6090 0.5588 0.075 Uiso 1 1 calc R . .
C21 C 0.4454(6) 0.6408(3) 0.5047(3) 0.0824(17) Uani 1 1 d . . .
H21 H 0.4619 0.6771 0.4562 0.099 Uiso 1 1 calc R . .
C22 C 0.3231(7) 0.6288(4) 0.5157(4) 0.093(2) Uani 1 1 d . . .
H22 H 0.2563 0.6578 0.4753 0.112 Uiso 1 1 calc R . .
C23 C 0.2980(5) 0.5738(4) 0.5862(4) 0.0879(17) Uani 1 1 d . . .
H23 H 0.2145 0.5657 0.5936 0.105 Uiso 1 1 calc R . .
C24 C 0.3982(4) 0.5301(3) 0.6468(3) 0.0671(13) Uani 1 1 d . . .
H24 H 0.3818 0.4921 0.6940 0.080 Uiso 1 1 calc R . .
F1 F 1.0903(4) 0.4114(2) 0.4966(2) 0.1290(14) Uani 1 1 d . . .
N1 N 1.0698(3) 0.3739(2) 1.0448(2) 0.0454(8) Uani 1 1 d . . .
N2 N 1.1821(3) 0.3867(2) 1.0126(2) 0.0529(9) Uani 1 1 d . . .
H2A H 1.2578 0.3871 1.0464 0.064 Uiso 1 1 calc R . .
N3 N 0.8435(3) 0.4210(2) 0.7580(2) 0.0453(8) Uani 1 1 d . . .
N4 N 0.7713(3) 0.4530(2) 0.8191(2) 0.0464(8) Uani 1 1 d . . .
H4A H 0.7996 0.4495 0.8781 0.056 Uiso 1 1 calc R . .
N5 N 0.6276(3) 0.4998(2) 0.6928(2) 0.0523(9) Uani 1 1 d . . .
H5A H 0.6819 0.4762 0.6636 0.063 Uiso 1 1 calc R . .
O1 O 0.8574(3) 0.3550(2) 0.97596(17) 0.0562(8) Uani 1 1 d . . .
S1 S 0.56534(10) 0.52295(9) 0.85925(7) 0.0623(4) 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
C1 C2 1.383(6) . ?
C1 C6 1.393(5) . ?
C1 H1 0.9300 . ?
C2 C3 1.372(7) . ?
C2 H2 0.9300 . ?
C3 C4 1.374(7) . ?
C3 H3 0.9300 . ?
C4 C5 1.384(6) . ?
C4 H4 0.9300 . ?
C5 C6 1.365(6) . ?
C5 H5 0.9300 . ?
C6 N1 1.418(5) . ?
C7 N2 1.340(4) . ?
C7 C9 1.375(5) . ?
C7 C8 1.494(6) . ?
C8 H8A 0.9600 . ?
C8 H8B 0.9600 . ?
C8 H8C 0.9600 . ?
C9 C10 1.423(5) . ?
C9 C11 1.471(5) . ?
C10 O1 1.254(4) . ?
C10 N1 1.376(4) . ?
C11 N3 1.292(4) . ?
C11 C12 1.492(5) . ?
C12 C17 1.385(5) . ?
C12 C13 1.387(5) . ?
C13 C14 1.361(6) . ?
C13 H13 0.9300 . ?
C14 C15 1.365(6) . ?
C14 F1 1.367(5) . ?
C15 C16 1.369(6) . ?
C15 H15 0.9300 . ?
C16 C17 1.375(6) . ?
C16 H16 0.9300 . ?
C17 H17 0.9300 . ?
C18 N5 1.333(5) . ?
C18 N4 1.343(5) . ?
C18 S1 1.673(4) . ?
C19 C24 1.364(6) . ?
C19 C20 1.373(6) . ?
C19 N5 1.426(5) . ?
C20 C21 1.376(6) . ?
C20 H20 0.9300 . ?
C21 C22 1.362(8) . ?
C21 H21 0.9300 . ?
C22 C23 1.374(8) . ?
C22 H22 0.9300 . ?
C23 C24 1.396(6) . ?
C23 H23 0.9300 . ?
C24 H24 0.9300 . ?
N1 N2 1.391(4) . ?
N2 H2A 0.8600 . ?
N3 N4 1.378(4) . ?
N4 H4A 0.8600 . ?
N5 H5A 0.8600 . ?

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
C2 C1 C6 118.8(5) . . ?
C2 C1 H1 120.6 . . ?
C6 C1 H1 120.6 . . ?
C3 C2 C1 120.3(5) . . ?
C3 C2 H2 119.8 . . ?
C1 C2 H2 119.8 . . ?
C2 C3 C4 120.1(5) . . ?
C2 C3 H3 120.0 . . ?
C4 C3 H3 120.0 . . ?
C3 C4 C5 120.5(5) . . ?
C3 C4 H4 119.8 . . ?
C5 C4 H4 119.8 . . ?
C6 C5 C4 119.1(5) . . ?
C6 C5 H5 120.4 . . ?
C4 C5 H5 120.4 . . ?
C5 C6 C1 121.1(4) . . ?
C5 C6 N1 119.2(4) . . ?
C1 C6 N1 119.7(4) . . ?
N2 C7 C9 109.2(3) . . ?
N2 C7 C8 117.2(4) . . ?
C9 C7 C8 133.6(4) . . ?
C7 C8 H8A 109.5 . . ?
C7 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
C7 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
C7 C9 C10 107.2(3) . . ?
C7 C9 C11 125.0(3) . . ?
C10 C9 C11 127.7(3) . . ?
O1 C10 N1 122.7(4) . . ?
O1 C10 C9 130.8(3) . . ?
N1 C10 C9 106.5(3) . . ?
N3 C11 C9 128.0(3) . . ?
N3 C11 C12 114.0(3) . . ?
C9 C11 C12 117.9(3) . . ?
C17 C12 C13 119.2(4) . . ?
C17 C12 C11 119.9(3) . . ?
C13 C12 C11 120.9(4) . . ?
C14 C13 C12 118.2(4) . . ?
C14 C13 H13 120.9 . . ?
C12 C13 H13 120.9 . . ?
C13 C14 C15 123.6(4) . . ?
C13 C14 F1 118.1(4) . . ?
C15 C14 F1 118.3(4) . . ?
C14 C15 C16 117.8(4) . . ?
C14 C15 H15 121.1 . . ?
C16 C15 H15 121.1 . . ?
C15 C16 C17 120.7(4) . . ?
C15 C16 H16 119.7 . . ?
C17 C16 H16 119.7 . . ?
C16 C17 C12 120.4(4) . . ?
C16 C17 H17 119.8 . . ?
C12 C17 H17 119.8 . . ?
N5 C18 N4 115.2(4) . . ?
N5 C18 S1 126.1(3) . . ?
N4 C18 S1 118.6(3) . . ?
C24 C19 C20 120.4(4) . . ?
C24 C19 N5 122.8(4) . . ?
C20 C19 N5 116.8(4) . . ?
C19 C20 C21 120.2(5) . . ?
C19 C20 H20 119.9 . . ?
C21 C20 H20 119.9 . . ?
C22 C21 C20 120.0(5) . . ?
C22 C21 H21 120.0 . . ?
C20 C21 H21 120.0 . . ?
C21 C22 C23 120.2(5) . . ?
C21 C22 H22 119.9 . . ?
C23 C22 H22 119.9 . . ?
C22 C23 C24 120.0(5) . . ?
C22 C23 H23 120.0 . . ?
C24 C23 H23 120.0 . . ?
C19 C24 C23 119.2(5) . . ?
C19 C24 H24 120.4 . . ?
C23 C24 H24 120.4 . . ?
C10 N1 N2 108.0(3) . . ?
C10 N1 C6 129.7(3) . . ?
N2 N1 C6 120.2(3) . . ?
C7 N2 N1 108.9(3) . . ?
C7 N2 H2A 125.5 . . ?
N1 N2 H2A 125.5 . . ?
C11 N3 N4 118.2(3) . . ?
C18 N4 N3 118.8(3) . . ?
C18 N4 H4A 120.6 . . ?
N3 N4 H4A 120.6 . . ?
C18 N5 C19 129.5(4) . . ?
C18 N5 H5A 115.3 . . ?
C19 N5 H5A 115.3 . . ?

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
N4 H4A O1 0.86 1.99 2.702(4) 139.8 .
N5 H5A N3 0.86 2.14 2.578(4) 111.2 .
N2 H2A S1 0.86 2.47 3.237(3) 148.4 3_767

_diffrn_measured_fraction_theta_max 0.979
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.979
_refine_diff_density_max         0.643
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.051
_chemical_properties_physical    ', Light-sensitive'
