# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_CG9114
_database_code_depnum_ccdc_archive 'CCDC 1428720'
_audit_update_record             
;
2015-09-30 deposited with the CCDC.	2020-10-12 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014

_chemical_name_systematic        
;
Methyl-2-(1-(4-(methylsulfonyl)phenyl)-3-phenyl-1H-pyrazol-5-yl)acetate
;

_chemical_melting_point_lt       365.5
_chemical_melting_point_gt       364.5

_chemical_formula_moiety         'C19 H18 N2 O4 S'
_chemical_formula_sum            'C19 H18 N2 O4 S'
_chemical_formula_weight         370.41

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0034 0.0017 '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 0.0066 0.0034 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0114 0.0062 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1265 0.1256 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 2yc'

_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.
;

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                   28.442(1)
_cell_length_b                   11.1139(4)
_cell_length_c                   11.4467(4)
_cell_angle_alpha                90
_cell_angle_beta                 90.780(2)
_cell_angle_gamma                90
_cell_volume                     3618.0(2)
_cell_formula_units_Z            8
_cell_measurement_temperature    123(2)

_cell_measurement_reflns_used    9853

_cell_measurement_theta_min      2.65

_cell_measurement_theta_max      36.01


_exptl_crystal_description       plate

_exptl_crystal_colour            colourless

_exptl_crystal_density_diffrn    1.360
_exptl_crystal_F_000             1552

_exptl_transmission_factor_min   0.6999
_exptl_transmission_factor_max   0.7471

_exptl_crystal_size_max          0.350
_exptl_crystal_size_mid          0.280
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    0.203
_shelx_estimated_absorpt_T_min   0.932
_shelx_estimated_absorpt_T_max   0.976
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Brunker-Nonium SDABS'



_diffrn_ambient_temperature      123(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   sealed-tube
_diffrn_measurement_device_type  'Bruker APEX-II CCD'

_diffrn_radiation_monochromator  graphite

_diffrn_measurement_method       'φ and ω scans'
_diffrn_reflns_number            52794
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         2.646
_diffrn_reflns_theta_max         36.147
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             8655
_reflns_number_gt                7227
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;

_computing_data_collection       'Bruker APEX2'

_computing_cell_refinement       'Bruker SAINT'

_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'

_computing_publication_material  'Bruker SHELXTL'


_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0644P)²+0.9217P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         8655
_refine_ls_number_parameters     307
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0358
_refine_ls_wR_factor_ref         0.1124
_refine_ls_wR_factor_gt          0.1041
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_restrained_S_all      1.033
_refine_ls_shift/su_max          0.001
_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_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
N1 N 0.22198(2) 0.59918(6) 0.64554(5) 0.02243(10) Uani 1 1 d . . . . .
N2 N 0.18806(2) 0.58706(6) 0.56156(6) 0.02412(11) Uani 1 1 d . . . . .
C1 C 0.14884(2) 0.62677(7) 0.61153(7) 0.02448(12) Uani 1 1 d . . . . .
C2 C 0.15782(3) 0.66580(7) 0.72722(7) 0.02616(13) Uani 1 1 d . . . . .
H2 H 0.1359(4) 0.6984(12) 0.7839(11) 0.035(3) Uiso 1 1 d . . . . .
C3 C 0.20522(3) 0.64770(7) 0.74650(6) 0.02437(12) Uani 1 1 d . . . . .
C4 C 0.23538(3) 0.67771(8) 0.85022(6) 0.02911(14) Uani 1 1 d . . . . .
H4A H 0.2179(5) 0.7298(13) 0.9045(12) 0.042(3) Uiso 1 1 d . . . . .
H4B H 0.2430(5) 0.6027(13) 0.8942(12) 0.040(3) Uiso 1 1 d . . . . .
C5 C 0.27913(3) 0.74781(7) 0.81831(6) 0.02642(13) Uani 1 1 d . . . . .
O1 O 0.28234(2) 0.81348(6) 0.73517(5) 0.03081(12) Uani 1 1 d . . . . .
O2 O 0.31390(2) 0.72813(6) 0.89594(5) 0.03304(13) Uani 1 1 d . . . . .
C6 C 0.35743(4) 0.79077(10) 0.87155(11) 0.0424(2) Uani 1 1 d . . . . .
H6A H 0.3765(6) 0.7720(16) 0.9377(14) 0.058(4) Uiso 1 1 d . . . . .
H6B H 0.3515(5) 0.8720(16) 0.8690(14) 0.052(4) Uiso 1 1 d . . . . .
H6C H 0.3701(6) 0.7614(16) 0.7961(14) 0.056(4) Uiso 1 1 d . . . . .
C7 C 0.26899(2) 0.56762(6) 0.61953(6) 0.02021(11) Uani 1 1 d . . . . .
C8 C 0.28841(2) 0.60598(6) 0.51491(6) 0.02252(12) Uani 1 1 d . . . . .
H8 H 0.2697(4) 0.6506(11) 0.4628(10) 0.027(3) Uiso 1 1 d . . . . .
C9 C 0.33507(3) 0.57810(7) 0.49227(6) 0.02325(12) Uani 1 1 d . . . . .
H9 H 0.3503(4) 0.6066(11) 0.4222(11) 0.031(3) Uiso 1 1 d . . . . .
C10 C 0.36096(2) 0.51116(6) 0.57297(6) 0.02079(11) Uani 1 1 d . . . . .
C11 C 0.34141(2) 0.47280(7) 0.67687(6) 0.02391(12) Uani 1 1 d . . . . .
H11 H 0.3608(5) 0.4250(12) 0.7294(12) 0.037(3) Uiso 1 1 d . . . . .
C12 C 0.29496(2) 0.50077(7) 0.70030(6) 0.02368(12) Uani 1 1 d . . . . .
H12 H 0.2809(5) 0.4708(12) 0.7711(12) 0.038(3) Uiso 1 1 d . . . . .
S1 S 0.41953(2) 0.46956(2) 0.54591(2) 0.02714(5) Uani 1 1 d . . . . .
C13 C 0.45304(3) 0.56762(11) 0.63409(8) 0.0377(2) Uani 1 1 d . . . . .
H13A H 0.4456(6) 0.5519(15) 0.7182(14) 0.052(4) Uiso 1 1 d . . . . .
H13B H 0.4466(6) 0.6483(17) 0.6031(15) 0.063(5) Uiso 1 1 d . . . . .
H13C H 0.4854(6) 0.5452(15) 0.6211(15) 0.054(4) Uiso 1 1 d . . . . .
O3 O 0.42920(2) 0.49377(8) 0.42488(5) 0.03867(15) Uani 1 1 d . . . . .
O4 O 0.42590(2) 0.34866(7) 0.58900(7) 0.04029(15) Uani 1 1 d . . . . .
C14 C 0.10392(3) 0.62588(7) 0.54636(8) 0.02866(14) Uani 1 1 d . . . . .
C15 C 0.10138(3) 0.57905(9) 0.43326(9) 0.03735(18) Uani 1 1 d . . . . .
H15 H 0.1299(5) 0.5438(14) 0.3926(13) 0.045(4) Uiso 1 1 d . . . . .
C16 C 0.05860(4) 0.57646(11) 0.37242(12) 0.0474(3) Uani 1 1 d . . . . .
H16 H 0.0576(7) 0.5443(16) 0.2907(16) 0.065(5) Uiso 1 1 d . . . . .
C17 C 0.01839(4) 0.62200(10) 0.42362(13) 0.0492(3) Uani 1 1 d . . . . .
H17 H -0.0119(6) 0.6213(16) 0.3825(14) 0.056(4) Uiso 1 1 d . . . . .
C18 C 0.02060(3) 0.66959(10) 0.53497(12) 0.0450(2) Uani 1 1 d . . . . .
H18 H -0.0047(6) 0.6988(14) 0.5695(13) 0.050(4) Uiso 1 1 d . . . . .
C19 C 0.06321(3) 0.67172(8) 0.59702(10) 0.03517(17) Uani 1 1 d . . . . .
H19 H 0.0643(4) 0.7061(12) 0.6777(12) 0.037(3) Uiso 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
N1 N2 1.3593(8) .
N1 C3 1.3671(9) .
N1 C7 1.4176(9) .
N2 C1 1.3355(9) .
C1 C2 1.4134(11) .
C1 C14 1.4707(10) .
C2 C3 1.3778(10) .
C2 H2 0.976(13) .
C3 C4 1.4930(11) .
C4 C5 1.5170(12) .
C4 H4A 0.987(14) .
C4 H4B 0.997(14) .
C5 O1 1.2037(10) .
C5 O2 1.3385(9) .
O2 C6 1.4507(13) .
C6 H6A 0.949(16) .
C6 H6B 0.919(18) .
C6 H6C 0.996(16) .
C7 C12 1.3907(9) .
C7 C8 1.3925(9) .
C8 C9 1.3905(10) .
C8 H8 0.937(12) .
C9 C10 1.3895(10) .
C9 H9 0.970(13) .
C10 C11 1.3869(10) .
C10 S1 1.7605(7) .
C11 C12 1.3870(10) .
C11 H11 0.969(14) .
C12 H12 0.967(14) .
S1 O3 1.4414(7) .
S1 O4 1.4419(8) .
S1 C13 1.7575(10) .
C13 H13A 1.004(16) .
C13 H13B 0.981(19) .
C13 H13C 0.966(16) .
C14 C15 1.3963(14) .
C14 C19 1.3982(12) .
C15 C16 1.3938(13) .
C15 H15 1.020(15) .
C16 C17 1.3878(18) .
C16 H16 1.001(19) .
C17 C18 1.3806(19) .
C17 H17 0.976(16) .
C18 C19 1.3964(13) .
C18 H18 0.888(16) .
C19 H19 0.999(13) .

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
N2 N1 C3 112.61(6) . .
N2 N1 C7 119.29(6) . .
C3 N1 C7 128.03(6) . .
C1 N2 N1 104.67(6) . .
N2 C1 C2 111.18(6) . .
N2 C1 C14 120.36(7) . .
C2 C1 C14 128.46(7) . .
C3 C2 C1 105.62(6) . .
C3 C2 H2 125.5(8) . .
C1 C2 H2 128.9(8) . .
N1 C3 C2 105.90(6) . .
N1 C3 C4 123.85(6) . .
C2 C3 C4 130.18(7) . .
C3 C4 C5 112.81(6) . .
C3 C4 H4A 110.0(8) . .
C5 C4 H4A 105.7(8) . .
C3 C4 H4B 109.5(8) . .
C5 C4 H4B 112.2(8) . .
H4A C4 H4B 106.3(11) . .
O1 C5 O2 124.11(8) . .
O1 C5 C4 124.95(7) . .
O2 C5 C4 110.93(7) . .
C5 O2 C6 114.74(7) . .
O2 C6 H6A 102.7(10) . .
O2 C6 H6B 108.8(10) . .
H6A C6 H6B 110.1(14) . .
O2 C6 H6C 109.2(10) . .
H6A C6 H6C 114.3(14) . .
H6B C6 H6C 111.3(14) . .
C12 C7 C8 121.46(6) . .
C12 C7 N1 119.11(6) . .
C8 C7 N1 119.42(6) . .
C9 C8 C7 118.87(6) . .
C9 C8 H8 122.4(7) . .
C7 C8 H8 118.8(7) . .
C10 C9 C8 119.60(6) . .
C10 C9 H9 119.1(7) . .
C8 C9 H9 121.2(7) . .
C11 C10 C9 121.31(6) . .
C11 C10 S1 117.49(5) . .
C9 C10 S1 121.20(5) . .
C10 C11 C12 119.41(6) . .
C10 C11 H11 118.0(8) . .
C12 C11 H11 122.6(8) . .
C11 C12 C7 119.34(6) . .
C11 C12 H12 119.4(8) . .
C7 C12 H12 121.3(8) . .
O3 S1 O4 118.56(5) . .
O3 S1 C13 109.11(5) . .
O4 S1 C13 108.47(5) . .
O3 S1 C10 108.26(4) . .
O4 S1 C10 107.41(4) . .
C13 S1 C10 104.07(4) . .
S1 C13 H13A 108.8(9) . .
S1 C13 H13B 105.2(10) . .
H13A C13 H13B 117.8(14) . .
S1 C13 H13C 105.1(10) . .
H13A C13 H13C 108.4(14) . .
H13B C13 H13C 110.7(14) . .
C15 C14 C19 119.18(8) . .
C15 C14 C1 120.44(7) . .
C19 C14 C1 120.39(8) . .
C16 C15 C14 120.32(10) . .
C16 C15 H15 117.4(8) . .
C14 C15 H15 122.3(8) . .
C17 C16 C15 120.01(11) . .
C17 C16 H16 120.8(11) . .
C15 C16 H16 119.1(11) . .
C18 C17 C16 120.14(9) . .
C18 C17 H17 118.5(10) . .
C16 C17 H17 121.4(10) . .
C17 C18 C19 120.29(10) . .
C17 C18 H18 121.6(10) . .
C19 C18 H18 118.1(10) . .
C18 C19 C14 120.05(10) . .
C18 C19 H19 119.5(7) . .
C14 C19 H19 120.5(7) . .

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
C4 H4A O2 0.987(14) 2.513(14) 3.4080(10) 150.6(11) 7_567
C6 H6A O4 0.949(16) 2.589(17) 3.5010(13) 161.2(14) 6_566
C12 H12 O1 0.967(14) 2.509(13) 3.1234(10) 121.3(10) 4_546
C13 H13A O3 1.004(16) 2.470(16) 3.4736(11) 177.8(14) 6_566
C13 H13C O3 0.966(16) 2.530(17) 3.4930(11) 174.1(14) 5_666

_refine_diff_density_max         0.529
_refine_diff_density_min         -0.458
_refine_diff_density_rms         0.051

_shelxl_version_number           2014-1

####################################################################### 
# 
# 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_CG1415
_database_code_depnum_ccdc_archive 'CCDC 1433314'
_audit_update_record             
;
2015-10-26 deposited with the CCDC.	2020-10-12 downloaded from the CCDC.
;


_audit_creation_method           SHELXL-2014

_chemical_name_systematic        
;
3-(2-Fluoroethyl)-1-(4-(methylsulfonyl)phenyl)-5-phenyl-1H-pyrazole
;

_chemical_formula_moiety         'C18 H17 F N2 O2 S'
_chemical_formula_sum            'C18 H17 F N2 O2 S'
_chemical_formula_weight         344.39

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0034 0.0017 '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 0.0066 0.0034 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0114 0.0062 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0180 0.0106 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1265 0.1256 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   11.2831(3)
_cell_length_b                   11.9926(3)
_cell_length_c                   14.2709(4)
_cell_angle_alpha                92.663(1)
_cell_angle_beta                 105.904(1)
_cell_angle_gamma                115.409(1)
_cell_volume                     1647.31(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    123(2)

_cell_measurement_reflns_used    9756
_cell_measurement_theta_min      3.07
_cell_measurement_theta_max      36.88
_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_F_000             720

_exptl_transmission_factor_min   0.7104
_exptl_transmission_factor_max   0.7472
_exptl_crystal_size_max          0.350
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    0.217
_shelx_estimated_absorpt_T_min   0.928
_shelx_estimated_absorpt_T_max   0.979
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Bruker-Nonius SADABS'



_diffrn_ambient_temperature      123(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'Bruker-Nonius APEX-II CCD'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_method       'φ and ω scans'
_diffrn_reflns_number            59598
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_av_R_equivalents  0.0287
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         1.914
_diffrn_reflns_theta_max         36.903
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             16365
_reflns_number_gt                13574
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0616P)²+0.3394P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         16365
_refine_ls_number_parameters     452
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0491
_refine_ls_R_factor_gt           0.0391
_refine_ls_wR_factor_ref         0.1149
_refine_ls_wR_factor_gt          0.1069
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_restrained_S_all      1.032
_refine_ls_shift/su_max          0.003
_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_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
N1 N 0.81108(6) 0.40706(6) 0.35697(5) 0.01568(10) Uani 1 1 d . . . . .
N2 N 0.69524(7) 0.35854(6) 0.38569(5) 0.01718(11) Uani 1 1 d . . . . .
C1 C 0.63777(7) 0.23498(7) 0.35517(6) 0.01753(12) Uani 1 1 d . . . . .
C2 C 0.71527(8) 0.20222(7) 0.30693(6) 0.01834(12) Uani 1 1 d . . . . .
H2A H 0.6957 0.1201 0.2793 0.022 Uiso 1 1 calc R U . . .
C3 C 0.82526(7) 0.31417(7) 0.30821(5) 0.01618(11) Uani 1 1 d . . . . .
C4 C 0.50711(8) 0.15015(8) 0.37486(7) 0.02174(14) Uani 1 1 d . . . . .
H4A H 0.4531 0.1963 0.3775 0.026 Uiso 1 1 calc R U . . .
H4B H 0.5317 0.1266 0.4403 0.026 Uiso 1 1 calc R U . . .
C5 C 0.41854(9) 0.03283(9) 0.29677(8) 0.02826(17) Uani 1 1 d . . . . .
H5A H 0.4736 -0.0111 0.2903 0.034 Uiso 1 1 calc R U . . .
H5B H 0.3389 -0.0245 0.3162 0.034 Uiso 1 1 calc R U . . .
F1 F 0.36991(7) 0.06484(7) 0.20544(5) 0.04147(16) Uani 1 1 d . . . . .
C6 C 0.89993(7) 0.53827(6) 0.38639(5) 0.01494(11) Uani 1 1 d . . . . .
C7 C 0.84288(7) 0.61719(7) 0.40337(6) 0.01731(12) Uani 1 1 d . . . . .
H7A H 0.7464 0.5830 0.3941 0.021 Uiso 1 1 calc R U . . .
C8 C 0.92809(8) 0.74588(7) 0.43396(6) 0.01817(12) Uani 1 1 d . . . . .
H8A H 0.8908 0.8001 0.4471 0.022 Uiso 1 1 calc R U . . .
C9 C 1.06913(7) 0.79484(7) 0.44530(5) 0.01628(11) Uani 1 1 d . . . . .
C10 C 1.12586(7) 0.71670(7) 0.42792(6) 0.01661(11) Uani 1 1 d . . . . .
H10B H 1.2216 0.7514 0.4349 0.020 Uiso 1 1 calc R U . . .
C11 C 1.04176(7) 0.58739(7) 0.40028(6) 0.01641(11) Uani 1 1 d . . . . .
H11A H 1.0804 0.5329 0.3909 0.020 Uiso 1 1 calc R U . . .
S1 S 1.17910(2) 0.95753(2) 0.48764(2) 0.01786(4) Uani 1 1 d . . . . .
O1 O 1.14836(7) 0.99732(6) 0.57119(5) 0.02423(12) Uani 1 1 d . . . . .
O2 O 1.31966(6) 0.98035(6) 0.50171(5) 0.02468(12) Uani 1 1 d . . . . .
C12 C 1.12957(9) 1.02947(8) 0.38968(7) 0.02395(15) Uani 1 1 d . . . . .
H12A H 1.1873 1.1208 0.4086 0.036 Uiso 1 1 calc R U . . .
H12B H 1.0318 1.0093 0.3757 0.036 Uiso 1 1 calc R U . . .
H12C H 1.1421 0.9983 0.3303 0.036 Uiso 1 1 calc R U . . .
C13 C 0.92994(8) 0.33368(7) 0.25913(6) 0.01723(12) Uani 1 1 d . . . . .
C14 C 0.95134(8) 0.41495(8) 0.19130(6) 0.02028(13) Uani 1 1 d . . . . .
H14A H 0.8999 0.4610 0.1778 0.024 Uiso 1 1 calc R U . . .
C15 C 1.04775(10) 0.42867(9) 0.14348(7) 0.02611(16) Uani 1 1 d . . . . .
H15A H 1.0625 0.4845 0.0980 0.031 Uiso 1 1 calc R U . . .
C16 C 1.12255(10) 0.36064(9) 0.16226(9) 0.03050(19) Uani 1 1 d . . . . .
H16A H 1.1885 0.3702 0.1298 0.037 Uiso 1 1 calc R U . . .
C17 C 1.10047(11) 0.27903(10) 0.22844(9) 0.03163(19) Uani 1 1 d . . . . .
H17A H 1.1513 0.2324 0.2411 0.038 Uiso 1 1 calc R U . . .
C18 C 1.00422(9) 0.26476(8) 0.27669(7) 0.02488(15) Uani 1 1 d . . . . .
H18A H 0.9892 0.2081 0.3216 0.030 Uiso 1 1 calc R U . . .
N3 N 0.60361(7) 0.56925(7) 0.18171(5) 0.01904(11) Uani 1 1 d . . . . .
N4 N 0.50379(8) 0.53195(9) 0.22716(6) 0.02585(15) Uani 1 1 d . . . . .
C21 C 0.51892(9) 0.63840(12) 0.27385(7) 0.0307(2) Uani 1 1 d . . . . .
C22 C 0.62662(9) 0.74419(10) 0.25933(7) 0.02750(17) Uani 1 1 d . . . . .
H22A H 0.6564 0.8299 0.2847 0.033 Uiso 1 1 calc R U . . .
C23 C 0.68024(8) 0.69804(8) 0.20060(6) 0.01976(13) Uani 1 1 d . . . . .
C24A C 0.43241(16) 0.6457(2) 0.33470(12) 0.0317(3) Uani 0.781(3) 1 d . . P A 1
H24A H 0.3327 0.5976 0.2953 0.038 Uiso 0.781(3) 1 d R U P A 1
H24B H 0.4535 0.7344 0.3532 0.038 Uiso 0.781(3) 1 d R U P A 1
C25A C 0.46302(17) 0.59315(14) 0.42771(11) 0.0378(4) Uani 0.781(3) 1 d . . P A
1
H25A H 0.4519 0.5076 0.4102 0.045 Uiso 0.781(3) 1 d R U P A 1
H25B H 0.3980 0.5882 0.4638 0.045 Uiso 0.781(3) 1 d R U P A 1
F2A F 0.60120(8) 0.67489(9) 0.48756(5) 0.04774(19) Uani 0.781(3) 1 d . . P A 1
C24B C 0.4158(5) 0.5965(5) 0.3355(4) 0.0221(9) Uani 0.219(3) 1 d . . P A 2
H24C H 0.3270 0.5874 0.2964 0.026 Uiso 0.219(3) 1 d R U P A 2
H24D H 0.4040 0.5177 0.3548 0.026 Uiso 0.219(3) 1 d R U P A 2
C25B C 0.4766(4) 0.6964(4) 0.4225(3) 0.0237(9) Uani 0.219(3) 1 d . . P A 2
H25C H 0.5098 0.7781 0.4050 0.028 Uiso 0.219(3) 1 d R U P A 2
H25D H 0.4115 0.6872 0.4568 0.028 Uiso 0.219(3) 1 d R U P A 2
F2B F 0.60120(8) 0.67489(9) 0.48756(5) 0.04774(19) Uani 0.219(3) 1 d . . P A 2
C26 C 0.60698(7) 0.47573(7) 0.11986(5) 0.01691(12) Uani 1 1 d . . . . .
C27 C 0.55772(8) 0.35371(8) 0.13929(6) 0.02128(13) Uani 1 1 d . . . . .
H27A H 0.5236 0.3349 0.1935 0.026 Uiso 1 1 calc R U . . .
C28 C 0.55874(9) 0.25992(8) 0.07921(6) 0.02200(14) Uani 1 1 d . . . . .
H28A H 0.5237 0.1764 0.0912 0.026 Uiso 1 1 calc R U . . .
C29 C 0.61167(8) 0.28943(7) 0.00101(6) 0.01872(12) Uani 1 1 d . . . . .
C30 C 0.65900(8) 0.41029(7) -0.01959(6) 0.01772(12) Uani 1 1 d . . . . .
H30A H 0.6943 0.4291 -0.0733 0.021 Uiso 1 1 calc R U . . .
C31 C 0.65435(8) 0.50329(7) 0.03872(6) 0.01729(12) Uani 1 1 d . . . . .
H31A H 0.6832 0.5853 0.0236 0.021 Uiso 1 1 calc R U . . .
S2 S 0.61776(2) 0.17284(2) -0.07477(2) 0.02131(4) Uani 1 1 d . . . . .
O3 O 0.48078(7) 0.06678(6) -0.11227(6) 0.02775(13) Uani 1 1 d . . . . .
O4 O 0.68392(7) 0.23134(7) -0.14503(5) 0.02735(13) Uani 1 1 d . . . . .
C32 C 0.72685(10) 0.12448(9) 0.00747(8) 0.02872(18) Uani 1 1 d . . . . .
H32A H 0.7355 0.0588 -0.0293 0.043 Uiso 1 1 calc R U . . .
H32B H 0.6869 0.0914 0.0591 0.043 Uiso 1 1 calc R U . . .
H32C H 0.8188 0.1964 0.0382 0.043 Uiso 1 1 calc R U . . .
C33 C 0.80204(8) 0.77085(7) 0.17072(6) 0.01888(12) Uani 1 1 d . . . . .
C34 C 0.91019(8) 0.73872(8) 0.18290(6) 0.02019(13) Uani 1 1 d . . . . .
H34A H 0.9046 0.6660 0.2093 0.024 Uiso 1 1 calc R U . . .
C35 C 1.02569(9) 0.81278(9) 0.15656(7) 0.02482(15) Uani 1 1 d . . . . .
H35A H 1.0979 0.7897 0.1636 0.030 Uiso 1 1 calc R U . . .
C36 C 1.03534(10) 0.92089(10) 0.11984(8) 0.02947(18) Uani 1 1 d . . . . .
H36A H 1.1142 0.9716 0.1019 0.035 Uiso 1 1 calc R U . . .
C37 C 0.92956(10) 0.95444(9) 0.10942(8) 0.03058(18) Uani 1 1 d . . . . .
H37A H 0.9368 1.0287 0.0851 0.037 Uiso 1 1 calc R U . . .
C38 C 0.81330(9) 0.87998(8) 0.13439(7) 0.02549(16) Uani 1 1 d . . . . .
H38A H 0.7411 0.9033 0.1268 0.031 Uiso 1 1 calc R U . . .


_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
N1 N2 1.3705(9) .
N1 C3 1.3757(10) .
N1 C6 1.4183(9) .
N2 C1 1.3291(10) .
C1 C2 1.4116(11) .
C1 C4 1.5013(11) .
C2 C3 1.3778(10) .
C2 H2A 0.9500 .
C3 C13 1.4738(10) .
C4 C5 1.5025(13) .
C4 H4A 0.9900 .
C4 H4B 0.9900 .
C5 F1 1.4080(13) .
C5 H5A 0.9900 .
C5 H5B 0.9900 .
C6 C11 1.3977(10) .
C6 C7 1.3985(10) .
C7 C8 1.3896(10) .
C7 H7A 0.9500 .
C8 C9 1.3970(10) .
C8 H8A 0.9500 .
C9 C10 1.3890(10) .
C9 S1 1.7645(7) .
C10 C11 1.3915(10) .
C10 H10B 0.9500 .
C11 H11A 0.9500 .
S1 O2 1.4416(7) .
S1 O1 1.4441(7) .
S1 C12 1.7631(9) .
C12 H12A 0.9800 .
C12 H12B 0.9800 .
C12 H12C 0.9800 .
C13 C18 1.3953(11) .
C13 C14 1.3998(11) .
C14 C15 1.3927(12) .
C14 H14A 0.9500 .
C15 C16 1.3916(15) .
C15 H15A 0.9500 .
C16 C17 1.3848(15) .
C16 H16A 0.9500 .
C17 C18 1.3943(13) .
C17 H17A 0.9500 .
C18 H18A 0.9500 .
N3 N4 1.3727(10) .
N3 C23 1.3760(11) .
N3 C26 1.4147(10) .
N4 C21 1.3320(14) .
C21 C22 1.4031(16) .
C21 C24A 1.4986(16) .
C21 C24B 1.575(4) .
C22 C23 1.3772(11) .
C22 H22A 0.9500 .
C23 C33 1.4694(11) .
C24A C25A 1.514(3) .
C24A H24A 0.9900 .
C24A H24B 0.9900 .
C25A F2A 1.4149(18) .
C25A H25A 0.9901 .
C25A H25B 0.9899 .
C24B C25B 1.462(7) .
C24B H24C 0.9600 .
C24B H24D 0.9600 .
C25B H25C 0.9600 .
C25B H25D 0.9601 .
C26 C27 1.3969(11) .
C26 C31 1.3996(10) .
C27 C28 1.3883(13) .
C27 H27A 0.9500 .
C28 C29 1.3957(12) .
C28 H28A 0.9500 .
C29 C30 1.3906(11) .
C29 S2 1.7640(8) .
C30 C31 1.3882(11) .
C30 H30A 0.9500 .
C31 H31A 0.9500 .
S2 O4 1.4425(8) .
S2 O3 1.4456(7) .
S2 C32 1.7644(9) .
C32 H32A 0.9800 .
C32 H32B 0.9800 .
C32 H32C 0.9800 .
C33 C38 1.3980(12) .
C33 C34 1.4003(11) .
C34 C35 1.3909(12) .
C34 H34A 0.9500 .
C35 C36 1.3931(14) .
C35 H35A 0.9500 .
C36 C37 1.3889(15) .
C36 H36A 0.9500 .
C37 C38 1.3876(14) .
C37 H37A 0.9500 .
C38 H38A 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
N2 N1 C3 111.65(6) . .
N2 N1 C6 117.64(6) . .
C3 N1 C6 130.54(6) . .
C1 N2 N1 105.00(6) . .
N2 C1 C2 111.52(7) . .
N2 C1 C4 119.86(7) . .
C2 C1 C4 128.62(7) . .
C3 C2 C1 105.62(7) . .
C3 C2 H2A 127.2 . .
C1 C2 H2A 127.2 . .
N1 C3 C2 106.20(6) . .
N1 C3 C13 125.99(6) . .
C2 C3 C13 127.56(7) . .
C1 C4 C5 112.35(7) . .
C1 C4 H4A 109.1 . .
C5 C4 H4A 109.1 . .
C1 C4 H4B 109.1 . .
C5 C4 H4B 109.1 . .
H4A C4 H4B 107.9 . .
F1 C5 C4 109.45(8) . .
F1 C5 H5A 109.8 . .
C4 C5 H5A 109.8 . .
F1 C5 H5B 109.8 . .
C4 C5 H5B 109.8 . .
H5A C5 H5B 108.2 . .
C11 C6 C7 120.72(6) . .
C11 C6 N1 120.83(6) . .
C7 C6 N1 118.44(6) . .
C8 C7 C6 119.60(7) . .
C8 C7 H7A 120.2 . .
C6 C7 H7A 120.2 . .
C7 C8 C9 119.45(7) . .
C7 C8 H8A 120.3 . .
C9 C8 H8A 120.3 . .
C10 C9 C8 121.03(7) . .
C10 C9 S1 119.15(5) . .
C8 C9 S1 119.75(6) . .
C9 C10 C11 119.71(7) . .
C9 C10 H10B 120.1 . .
C11 C10 H10B 120.1 . .
C10 C11 C6 119.44(7) . .
C10 C11 H11A 120.3 . .
C6 C11 H11A 120.3 . .
O2 S1 O1 118.17(4) . .
O2 S1 C12 108.45(4) . .
O1 S1 C12 107.97(4) . .
O2 S1 C9 108.17(4) . .
O1 S1 C9 108.02(4) . .
C12 S1 C9 105.36(4) . .
S1 C12 H12A 109.5 . .
S1 C12 H12B 109.5 . .
H12A C12 H12B 109.5 . .
S1 C12 H12C 109.5 . .
H12A C12 H12C 109.5 . .
H12B C12 H12C 109.5 . .
C18 C13 C14 119.22(7) . .
C18 C13 C3 119.29(7) . .
C14 C13 C3 121.40(7) . .
C15 C14 C13 120.30(8) . .
C15 C14 H14A 119.9 . .
C13 C14 H14A 119.9 . .
C16 C15 C14 120.11(8) . .
C16 C15 H15A 119.9 . .
C14 C15 H15A 119.9 . .
C17 C16 C15 119.76(8) . .
C17 C16 H16A 120.1 . .
C15 C16 H16A 120.1 . .
C16 C17 C18 120.53(9) . .
C16 C17 H17A 119.7 . .
C18 C17 H17A 119.7 . .
C17 C18 C13 120.07(8) . .
C17 C18 H18A 120.0 . .
C13 C18 H18A 120.0 . .
N4 N3 C23 111.39(7) . .
N4 N3 C26 118.01(7) . .
C23 N3 C26 130.45(7) . .
C21 N4 N3 104.87(8) . .
N4 C21 C22 111.71(8) . .
N4 C21 C24A 124.68(13) . .
C22 C21 C24A 123.61(12) . .
N4 C21 C24B 105.3(2) . .
C22 C21 C24B 142.5(2) . .
C23 C22 C21 105.71(9) . .
C23 C22 H22A 127.1 . .
C21 C22 H22A 127.1 . .
N3 C23 C22 106.32(8) . .
N3 C23 C33 126.63(7) . .
C22 C23 C33 126.88(8) . .
C21 C24A C25A 110.00(14) . .
C21 C24A H24A 109.8 . .
C25A C24A H24A 109.8 . .
C21 C24A H24B 109.5 . .
C25A C24A H24B 109.5 . .
H24A C24A H24B 108.1 . .
F2A C25A C24A 107.59(12) . .
F2A C25A H25A 110.4 . .
C24A C25A H25A 110.1 . .
F2A C25A H25B 110.2 . .
C24A C25A H25B 110.1 . .
H25A C25A H25B 108.5 . .
C25B C24B C21 106.4(3) . .
C25B C24B H24C 110.0 . .
C21 C24B H24C 109.9 . .
C25B C24B H24D 111.0 . .
C21 C24B H24D 110.8 . .
H24C C24B H24D 108.8 . .
C24B C25B H25C 111.6 . .
C24B C25B H25D 111.6 . .
H25C C25B H25D 109.2 . .
C27 C26 C31 120.33(7) . .
C27 C26 N3 118.70(7) . .
C31 C26 N3 120.94(7) . .
C28 C27 C26 119.86(7) . .
C28 C27 H27A 120.1 . .
C26 C27 H27A 120.1 . .
C27 C28 C29 119.42(7) . .
C27 C28 H28A 120.3 . .
C29 C28 H28A 120.3 . .
C30 C29 C28 120.97(7) . .
C30 C29 S2 118.67(6) . .
C28 C29 S2 120.35(6) . .
C31 C30 C29 119.62(7) . .
C31 C30 H30A 120.2 . .
C29 C30 H30A 120.2 . .
C30 C31 C26 119.70(7) . .
C30 C31 H31A 120.2 . .
C26 C31 H31A 120.2 . .
O4 S2 O3 118.47(4) . .
O4 S2 C29 108.14(4) . .
O3 S2 C29 108.63(4) . .
O4 S2 C32 108.72(5) . .
O3 S2 C32 107.64(4) . .
C29 S2 C32 104.36(4) . .
S2 C32 H32A 109.5 . .
S2 C32 H32B 109.5 . .
H32A C32 H32B 109.5 . .
S2 C32 H32C 109.5 . .
H32A C32 H32C 109.5 . .
H32B C32 H32C 109.5 . .
C38 C33 C34 119.24(8) . .
C38 C33 C23 118.37(7) . .
C34 C33 C23 122.28(7) . .
C35 C34 C33 120.30(8) . .
C35 C34 H34A 119.8 . .
C33 C34 H34A 119.8 . .
C34 C35 C36 119.93(8) . .
C34 C35 H35A 120.0 . .
C36 C35 H35A 120.0 . .
C37 C36 C35 119.97(9) . .
C37 C36 H36A 120.0 . .
C35 C36 H36A 120.0 . .
C38 C37 C36 120.32(9) . .
C38 C37 H37A 119.8 . .
C36 C37 H37A 119.8 . .
C37 C38 C33 120.23(8) . .
C37 C38 H38A 119.9 . .
C33 C38 H38A 119.9 . .

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
C4 H4B O2 0.99 2.51 3.2198(11) 128.0 2_766
C12 H12A F2A 0.98 2.57 3.4830(12) 155.1 2_776
C12 H12B O1 0.98 2.33 3.2189(11) 150.5 2_776
C22 H22A O1 0.95 2.57 3.3301(11) 137.7 2_776
C25A H25A F2A 0.99 2.63 3.3411(19) 128.7 2_666
C32 H32A F1 0.98 2.54 3.3154(13) 136.3 2_655
C32 H32B O3 0.98 2.36 3.2579(13) 151.2 2_655

_refine_diff_density_max         0.629
_refine_diff_density_min         -0.513
_refine_diff_density_rms         0.060

_shelxl_version_number           2014-1


_chemical_melting_point          99.5-101.5
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
