# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 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_sad
_database_code_depnum_ccdc_archive 'CCDC 1580610'
_audit_update_record             
;
2017-10-18 deposited with the CCDC.
2017-11-29 downloaded from the CCDC.
;
_audit_creation_date             2016-06-20
_audit_creation_method           
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_chemical_name_common            ?
_chemical_name_systematic        
2-((3-(4-nitrophenyl)-1-tosyl-1H-pyrazol-4-yl)methyl)benzonitrile
_chemical_formula_moiety         'C24 H18 N4 O4 S'
_chemical_formula_sum            'C24 H18 N4 O4 S'
_chemical_formula_weight         458.48
_chemical_absolute_configuration ?
_chemical_melting_point          403-406
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'
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           7
_space_group_name_H-M_alt        'P 1 c 1'
_space_group_name_Hall           'P -2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'x, -y, z+1/2'

_cell_length_a                   7.966(2)
_cell_length_b                   9.708(3)
_cell_length_c                   13.669(4)
_cell_angle_alpha                90
_cell_angle_beta                 98.158(5)
_cell_angle_gamma                90
_cell_volume                     1046.4(5)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    3465
_cell_measurement_temperature    203
_cell_measurement_theta_max      26.654
_cell_measurement_theta_min      2.582
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.196
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.915174
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS v.2.03 (Bruker,200?) was used for absorption correction.
R(int) was 0.0830 before and 0.0415 after correction.
The Ratio of minimum to maximum transmission is 0.9152.
The λ/2 correction factor is 0.0015.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             476
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0277
_diffrn_reflns_av_unetI/netI     0.0493
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8979
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.789
_diffrn_reflns_theta_min         2.098
_diffrn_ambient_temperature      203
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.896
_reflns_Friedel_fraction_full    0.947
_reflns_Friedel_fraction_max     0.890
_reflns_number_gt                4247
_reflns_number_total             4646
_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       'SAINT v6.28A (Bruker, 2002)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v6.28A (Bruker, 2002)'
_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    
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.233
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details 
;
 Flack x determined using 1726 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     299
_refine_ls_number_reflns         4646
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0468
_refine_ls_R_factor_gt           0.0423
_refine_ls_restrained_S_all      1.041
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0510P)²+0.0080P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0966
_refine_ls_wR_factor_ref         0.0990
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C19(H19), C5(H5), C8(H8), C24(H24), C6(H6), C12(H12), C9(H9),
 C13(H13), C15(H15), C14(H14), C23(H23), C20(H20)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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
S S -0.20950(10) -0.40291(8) -0.69098(6) 0.0316(2) Uani 1 1 d . . . . .
O2 O -0.2311(3) -0.4997(2) -0.61783(18) 0.0412(6) Uani 1 1 d . . . . .
N2 N -0.3657(3) -0.2314(3) -0.58821(19) 0.0290(6) Uani 1 1 d . . . . .
O4 O -0.7858(3) 0.1417(3) -0.25103(19) 0.0479(7) Uani 1 1 d . . . . .
N1 N -0.2368(3) -0.2484(3) -0.6405(2) 0.0302(6) Uani 1 1 d . . . . .
O1 O -0.0566(3) -0.3915(3) -0.7292(2) 0.0419(7) Uani 1 1 d . . . . .
O3 O -0.9837(3) 0.0827(3) -0.3638(2) 0.0490(7) Uani 1 1 d . . . . .
N3 N -0.8357(4) 0.0934(3) -0.3308(2) 0.0341(6) Uani 1 1 d . . . . .
C3 C -0.3566(4) -0.1011(3) -0.5627(2) 0.0262(6) Uani 1 1 d . . . . .
C11 C -0.1505(4) 0.1768(3) -0.6879(2) 0.0258(6) Uani 1 1 d . . . . .
C7 C -0.7113(4) 0.0440(3) -0.3902(2) 0.0273(6) Uani 1 1 d . . . . .
C1 C -0.1505(4) -0.1311(3) -0.6504(2) 0.0291(7) Uani 1 1 d . . . . .
H1 H -0.0571 -0.1195 -0.6858 0.035 Uiso 1 1 calc R . . . .
C2 C -0.2231(4) -0.0334(3) -0.6002(2) 0.0260(6) Uani 1 1 d . . . . .
C4 C -0.4794(4) -0.0476(3) -0.5029(2) 0.0261(6) Uani 1 1 d . . . . .
C19 C -0.3495(5) -0.3960(3) -0.8816(3) 0.0372(8) Uani 1 1 d . . . . .
H19 H -0.2390 -0.3772 -0.8966 0.045 Uiso 1 1 calc R . . . .
C5 C -0.4307(4) 0.0370(3) -0.4235(2) 0.0295(7) Uani 1 1 d . . . . .
H5 H -0.3154 0.0642 -0.4084 0.035 Uiso 1 1 calc R . . . .
C8 C -0.7639(4) -0.0410(4) -0.4683(2) 0.0322(7) Uani 1 1 d . . . . .
H8 H -0.8796 -0.0671 -0.4835 0.039 Uiso 1 1 calc R . . . .
C24 C -0.5379(4) -0.4387(4) -0.7633(3) 0.0367(8) Uani 1 1 d . . . . .
H24 H -0.5562 -0.4499 -0.6965 0.044 Uiso 1 1 calc R . . . .
C6 C -0.5466(4) 0.0827(3) -0.3661(2) 0.0291(7) Uani 1 1 d . . . . .
H6 H -0.5127 0.1401 -0.3105 0.035 Uiso 1 1 calc R . . . .
C12 C 0.0073(4) 0.1936(4) -0.7146(3) 0.0326(7) Uani 1 1 d . . . . .
H12 H 0.1045 0.1660 -0.6705 0.039 Uiso 1 1 calc R . . . .
C16 C -0.2882(4) 0.2185(3) -0.7531(2) 0.0291(7) Uani 1 1 d . . . . .
C10 C -0.1740(4) 0.1147(3) -0.5909(2) 0.0303(7) Uani 1 1 d . . . . .
H10A H -0.0670 0.1234 -0.5447 0.036 Uiso 1 1 calc R . . . .
H10B H -0.2629 0.1664 -0.5627 0.036 Uiso 1 1 calc R . . . .
C17 C -0.4530(5) 0.2063(4) -0.7256(3) 0.0366(8) Uani 1 1 d . . . . .
N4 N -0.5816(4) 0.1964(4) -0.7010(3) 0.0597(10) Uani 1 1 d . . . . .
C9 C -0.6466(4) -0.0871(4) -0.5237(2) 0.0315(7) Uani 1 1 d . . . . .
H9 H -0.6806 -0.1475 -0.5776 0.038 Uiso 1 1 calc R . . . .
C13 C 0.0269(5) 0.2499(3) -0.8046(3) 0.0390(9) Uani 1 1 d . . . . .
H13 H 0.1373 0.2612 -0.8220 0.047 Uiso 1 1 calc R . . . .
C18 C -0.3778(4) -0.4129(3) -0.7854(3) 0.0323(7) Uani 1 1 d . . . . .
C15 C -0.2687(5) 0.2739(3) -0.8441(2) 0.0365(8) Uani 1 1 d . . . . .
H15 H -0.3653 0.3009 -0.8890 0.044 Uiso 1 1 calc R . . . .
C14 C -0.1107(5) 0.2895(4) -0.8687(3) 0.0410(9) Uani 1 1 d . . . . .
H14 H -0.0963 0.3282 -0.9308 0.049 Uiso 1 1 calc R . . . .
C23 C -0.6696(5) -0.4481(4) -0.8377(3) 0.0469(9) Uani 1 1 d . . . . .
H23 H -0.7806 -0.4653 -0.8228 0.056 Uiso 1 1 calc R . . . .
C20 C -0.4842(6) -0.4070(4) -0.9549(3) 0.0471(10) Uani 1 1 d . . . . .
H20 H -0.4663 -0.3964 -1.0217 0.056 Uiso 1 1 calc R . . . .
C21 C -0.6441(6) -0.4330(4) -0.9345(3) 0.0478(9) Uani 1 1 d . . . . .
C22 C -0.7904(8) -0.4462(7) -1.0154(4) 0.0851(17) Uani 1 1 d . . . . .
H22A H -0.7842 -0.5351 -1.0486 0.128 Uiso 1 1 calc GR . . . .
H22B H -0.7860 -0.3715 -1.0633 0.128 Uiso 1 1 calc GR . . . .
H22C H -0.8968 -0.4404 -0.9874 0.128 Uiso 1 1 calc GR . . . .


_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
S O2 1.400(3) . ?
S N1 1.678(3) . ?
S O1 1.396(3) . ?
S C18 1.727(4) . ?
N2 N1 1.342(3) . ?
N2 C3 1.312(4) . ?
O4 N3 1.201(4) . ?
N1 C1 1.347(4) . ?
O3 N3 1.206(4) . ?
N3 C7 1.449(4) . ?
C3 C2 1.407(4) . ?
C3 C4 1.457(4) . ?
C11 C12 1.368(4) . ?
C11 C16 1.373(4) . ?
C11 C10 1.491(4) . ?
C7 C8 1.367(5) . ?
C7 C6 1.360(5) . ?
C1 C2 1.348(4) . ?
C2 C10 1.492(4) . ?
C4 C5 1.372(4) . ?
C4 C9 1.377(4) . ?
C19 C18 1.375(5) . ?
C19 C20 1.364(5) . ?
C5 C6 1.368(4) . ?
C8 C9 1.359(4) . ?
C24 C18 1.375(5) . ?
C24 C23 1.357(5) . ?
C12 C13 1.375(5) . ?
C16 C17 1.421(5) . ?
C16 C15 1.384(5) . ?
C17 N4 1.127(5) . ?
C13 C14 1.358(5) . ?
C15 C14 1.357(5) . ?
C23 C21 1.375(6) . ?
C20 C21 1.366(6) . ?
C21 C22 1.494(6) . ?

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
O2 S N1 105.64(15) . . ?
O2 S C18 109.57(16) . . ?
N1 S C18 103.05(15) . . ?
O1 S O2 121.53(16) . . ?
O1 S N1 104.70(14) . . ?
O1 S C18 110.52(16) . . ?
C3 N2 N1 104.0(3) . . ?
N2 N1 S 118.8(2) . . ?
N2 N1 C1 113.0(2) . . ?
C1 N1 S 128.1(2) . . ?
O4 N3 O3 123.6(3) . . ?
O4 N3 C7 118.3(3) . . ?
O3 N3 C7 118.1(3) . . ?
N2 C3 C2 111.7(3) . . ?
N2 C3 C4 118.5(3) . . ?
C2 C3 C4 129.8(3) . . ?
C12 C11 C16 118.1(3) . . ?
C12 C11 C10 121.4(3) . . ?
C16 C11 C10 120.5(3) . . ?
C8 C7 N3 118.7(3) . . ?
C6 C7 N3 119.1(3) . . ?
C6 C7 C8 122.3(3) . . ?
N1 C1 C2 106.3(3) . . ?
C3 C2 C10 128.5(3) . . ?
C1 C2 C3 104.9(3) . . ?
C1 C2 C10 126.5(3) . . ?
C5 C4 C3 121.4(3) . . ?
C5 C4 C9 119.2(3) . . ?
C9 C4 C3 119.4(3) . . ?
C20 C19 C18 118.3(4) . . ?
C6 C5 C4 120.7(3) . . ?
C9 C8 C7 118.4(3) . . ?
C23 C24 C18 119.3(3) . . ?
C7 C6 C5 118.6(3) . . ?
C11 C12 C13 120.8(3) . . ?
C11 C16 C17 119.1(3) . . ?
C11 C16 C15 121.1(3) . . ?
C15 C16 C17 119.7(3) . . ?
C2 C10 C11 112.2(3) . . ?
N4 C17 C16 178.0(4) . . ?
C8 C9 C4 120.9(3) . . ?
C14 C13 C12 120.4(3) . . ?
C19 C18 S 119.5(3) . . ?
C19 C18 C24 121.0(3) . . ?
C24 C18 S 119.5(3) . . ?
C14 C15 C16 119.5(3) . . ?
C15 C14 C13 120.0(3) . . ?
C24 C23 C21 120.7(4) . . ?
C19 C20 C21 121.6(4) . . ?
C23 C21 C22 119.8(5) . . ?
C20 C21 C23 119.1(4) . . ?
C20 C21 C22 121.1(4) . . ?

_shelx_SHELXL_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'
