# Supplementary Information (SI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# 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_SIFSIX-24-Zn
_database_code_depnum_ccdc_archive 'CCDC 2206134'
loop_
_audit_author_name
_audit_author_address
'Soumya Mukherjee'
;University of Limerick
Ireland
;
_audit_update_record             
;
2024-05-03 deposited with the CCDC.	2024-09-26 downloaded from the CCDC.
;
_audit_creation_date             2022-09-09
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
# end Validation Reply Form
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C14 H18 F6 N4 Si Zn'
_chemical_formula_sum            'C14 H18 F6 N4 Si Zn'
_chemical_formula_weight         449.78
_chemical_absolute_configuration Unknown
_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'
F F 0.0727 0.0534 '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'
Si Si 0.2541 0.3302 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn -1.5491 0.6778 '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      orthorhombic
_space_group_IT_number           20
_space_group_name_H-M_alt        'C 2 2 21'
_space_group_name_Hall           'C 2c 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'-x, y, -z+1/2'
'x, -y, -z'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z+1/2'
'-x+1/2, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   12.704(4)
_cell_length_b                   13.535(4)
_cell_length_c                   14.921(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2565.5(12)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    1361
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      51.928
_cell_measurement_theta_min      4.771
_shelx_estimated_absorpt_T_max   0.947
_shelx_estimated_absorpt_T_min   0.888
_exptl_absorpt_coefficient_mu    2.216
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.5370
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1014 before and 0.0820 after correction.
The Ratio of minimum to maximum transmission is 0.7145.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.165
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.055
_exptl_crystal_size_mid          0.036
_exptl_crystal_size_min          0.025
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1245
_diffrn_reflns_av_unetI/netI     0.1074
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6541
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        59.042
_diffrn_reflns_theta_max         59.042
_diffrn_reflns_theta_min         4.774
_diffrn_ambient_temperature      100.00
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker D8 Quest'
_diffrn_measurement_method       ?
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   ?
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_reflns_Friedel_coverage         0.722
_reflns_Friedel_fraction_full    0.955
_reflns_Friedel_fraction_max     0.953
_reflns_number_gt                1210
_reflns_number_total             1805
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         1.007
_refine_diff_density_min         -0.657
_refine_diff_density_rms         0.115
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.5(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.979
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     111
_refine_ls_number_reflns         1805
_refine_ls_number_restraints     41
_refine_ls_R_factor_all          0.1088
_refine_ls_R_factor_gt           0.0709
_refine_ls_restrained_S_all      0.990
_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)+(0.1129P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1692
_refine_ls_wR_factor_ref         0.1914
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.53427
 0.46573
2. Restrained distances
 H2-N2
 1 with sigma of 0.02
 C2-N2
 1.46 with sigma of 0.01
 H2-H1B = H2-H2B
 2.1 with sigma of 0.04
 C2-C7 \\sim C2-C4
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 N1, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4), C7(H7), C6(H6)
4.c Fitted hexagon refined as free rotating group:
 C5(C4,C3,C7,C6,N1)
;
_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
Zn1 Zn 0.55190(13) 0.500000 0.500000 0.0265(6) Uani 1 2 d S T P . .
Si1 Si 0.500000 0.5011(10) 0.750000 0.0399(11) Uani 1 2 d S T P . .
F1 F 0.5455(5) 0.5041(12) 0.6438(3) 0.060(2) Uani 1 1 d . . . . .
F2 F 0.5893(14) 0.5883(10) 0.7728(6) 0.078(6) Uani 1 1 d . . . . .
F3 F 0.4146(13) 0.4144(10) 0.7192(7) 0.069(4) Uani 1 1 d . . . . .
N2 N 0.9273(7) 0.8967(6) 0.5035(16) 0.045(3) Uani 1 1 d D . . . .
H2 H 0.952(4) 0.916(5) 0.443(3) 0.055 Uiso 1 1 d D U . . .
C1 C 0.8313(8) 0.9474(8) 0.502(2) 0.064(4) Uani 1 1 d . . . . .
H1A H 0.792136 0.928386 0.557032 0.077 Uiso 1 1 calc R U . . .
H1B H 0.790417 0.922648 0.450510 0.077 Uiso 1 1 calc DR U . . .
C2 C 0.9435(10) 0.7952(8) 0.514(2) 0.087(7) Uani 1 1 d D . . . .
H2A H 0.970172 0.782814 0.575421 0.105 Uiso 1 1 calc R U . . .
H2B H 0.998557 0.773577 0.471399 0.105 Uiso 1 1 calc DR U . . .
C5 C 0.7232(10) 0.6283(9) 0.5784(8) 0.056(5) Uani 1 1 d G . . . .
H5 H 0.699226 0.599477 0.632745 0.067 Uiso 1 1 calc R U . . .
C4 C 0.8101(10) 0.6907(9) 0.5787(11) 0.074(6) Uani 1 1 d DG . . . .
H4 H 0.845509 0.704542 0.633366 0.089 Uiso 1 1 calc R U . . .
C3 C 0.8451(6) 0.7328(6) 0.4992(14) 0.074(4) Uani 1 1 d G . . . .
C7 C 0.7932(11) 0.7125(9) 0.4192(11) 0.085(6) Uani 1 1 d DG . . . .
H7 H 0.817130 0.741280 0.364866 0.102 Uiso 1 1 calc R U . . .
C6 C 0.7063(11) 0.6501(8) 0.4189(8) 0.061(5) Uani 1 1 d G . . . .
H6 H 0.670848 0.636216 0.364243 0.073 Uiso 1 1 calc R U . . .
N1 N 0.6713(4) 0.6080(4) 0.4984(10) 0.0276(18) Uani 1 1 d G . . . .


_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
Zn1 F1 2.148(5) . ?
Zn1 F1 2.148(5) 4_566 ?
Zn1 N2 2.113(9) 5_445 ?
Zn1 N2 2.113(9) 8_466 ?
Zn1 H2 1.91(8) 5_445 ?
Zn1 N1 2.106(5) . ?
Zn1 N1 2.106(10) 4_566 ?
Si1 F1 1.687(5) 3_656 ?
Si1 F1 1.687(5) . ?
Si1 F2 1.671(16) . ?
Si1 F2 1.671(16) 3_656 ?
Si1 F3 1.663(15) . ?
Si1 F3 1.663(15) 3_656 ?
N2 H2 1.00(3) . ?
N2 C1 1.399(12) . ?
N2 C2 1.399(10) . ?
C1 C1 1.42(2) 4_576 ?
C1 H1A 0.9900 . ?
C1 H1B 0.9900 . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C2 C3 1.525(13) . ?
C5 H5 0.9500 . ?
C5 C4 1.3900 . ?
C5 N1 1.3900 . ?
C4 H4 0.9500 . ?
C4 C3 1.3900 . ?
C3 C7 1.3900 . ?
C7 H7 0.9500 . ?
C7 C6 1.3900 . ?
C6 H6 0.9500 . ?
C6 N1 1.3900 . ?

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
F1 Zn1 F1 175.7(3) . 4_566 ?
F1 Zn1 H2 60.7(11) 4_566 5_445 ?
F1 Zn1 H2 116.0(11) . 5_445 ?
N2 Zn1 F1 88.8(7) 8_466 . ?
N2 Zn1 F1 88.0(7) 8_466 4_566 ?
N2 Zn1 F1 88.8(7) 5_445 4_566 ?
N2 Zn1 F1 88.0(7) 5_445 . ?
N2 Zn1 N2 82.9(4) 5_445 8_466 ?
N2 Zn1 H2 28.1(8) 5_445 5_445 ?
N2 Zn1 H2 83.5(15) 8_466 5_445 ?
N1 Zn1 F1 92.0(6) . 4_566 ?
N1 Zn1 F1 91.2(10) 4_566 4_566 ?
N1 Zn1 F1 91.2(5) . . ?
N1 Zn1 F1 92.0(10) 4_566 . ?
N1 Zn1 N2 177.4(4) . 5_445 ?
N1 Zn1 N2 177.4(6) 4_566 8_466 ?
N1 Zn1 N2 94.6(3) . 8_466 ?
N1 Zn1 N2 94.6(4) 4_566 5_445 ?
N1 Zn1 H2 152.6(12) . 5_445 ?
N1 Zn1 H2 94.0(16) 4_566 5_445 ?
N1 Zn1 N1 87.9(5) . 4_566 ?
F1 Si1 F1 177.2(14) 3_656 . ?
F2 Si1 F1 86.6(7) 3_656 3_656 ?
F2 Si1 F1 91.4(6) . 3_656 ?
F2 Si1 F1 91.4(6) 3_656 . ?
F2 Si1 F1 86.6(7) . . ?
F2 Si1 F2 90.2(13) . 3_656 ?
F3 Si1 F1 93.0(8) . 3_656 ?
F3 Si1 F1 88.9(6) 3_656 3_656 ?
F3 Si1 F1 88.9(6) . . ?
F3 Si1 F1 93.0(8) 3_656 . ?
F3 Si1 F2 175.6(7) 3_656 3_656 ?
F3 Si1 F2 90.0(4) 3_656 . ?
F3 Si1 F2 175.6(7) . . ?
F3 Si1 F2 90.0(4) . 3_656 ?
F3 Si1 F3 90.2(12) 3_656 . ?
Si1 F1 Zn1 161.9(3) . . ?
Zn1 N2 H2 64(4) 5 . ?
C1 N2 Zn1 109.2(6) . 5 ?
C1 N2 H2 98(3) . . ?
C2 N2 Zn1 122.8(7) . 5 ?
C2 N2 H2 108(4) . . ?
C2 N2 C1 127.7(11) . . ?
N2 C1 C1 119.4(6) . 4_576 ?
N2 C1 H1A 107.5 . . ?
N2 C1 H1B 107.5 . . ?
C1 C1 H1A 107.5 4_576 . ?
C1 C1 H1B 107.5 4_576 . ?
H1A C1 H1B 107.0 . . ?
N2 C2 H2A 108.8 . . ?
N2 C2 H2B 108.8 . . ?
N2 C2 C3 114.0(10) . . ?
H2A C2 H2B 107.7 . . ?
C3 C2 H2A 108.8 . . ?
C3 C2 H2B 108.8 . . ?
C4 C5 H5 120.0 . . ?
C4 C5 N1 120.0 . . ?
N1 C5 H5 120.0 . . ?
C5 C4 H4 120.0 . . ?
C3 C4 C5 120.0 . . ?
C3 C4 H4 120.0 . . ?
C4 C3 C2 111.4(15) . . ?
C4 C3 C7 120.0 . . ?
C7 C3 C2 128.6(16) . . ?
C3 C7 H7 120.0 . . ?
C3 C7 C6 120.0 . . ?
C6 C7 H7 120.0 . . ?
C7 C6 H6 120.0 . . ?
N1 C6 C7 120.0 . . ?
N1 C6 H6 120.0 . . ?
C5 N1 Zn1 118.0(8) . . ?
C6 N1 Zn1 121.6(8) . . ?
C6 N1 C5 120.0 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Zn1 N2 C1 C1 1(5) 5 . . 4_576 ?
Zn1 N2 C2 C3 -170.3(15) 5 . . . ?
F2 Si1 F1 Zn1 -54(3) 3_656 . . . ?
F2 Si1 F1 Zn1 -144(3) . . . . ?
F3 Si1 F1 Zn1 36(3) . . . . ?
F3 Si1 F1 Zn1 126(3) 3_656 . . . ?
N2 C2 C3 C4 -111(2) . . . . ?
N2 C2 C3 C7 72(2) . . . . ?
C1 N2 C2 C3 16(5) . . . . ?
C2 N2 C1 C1 175(3) . . . 4_576 ?
C2 C3 C7 C6 177.3(10) . . . . ?
C5 C4 C3 C2 -177.8(8) . . . . ?
C5 C4 C3 C7 0.0 . . . . ?
C4 C5 N1 Zn1 172.9(5) . . . . ?
C4 C5 N1 C6 0.0 . . . . ?
C4 C3 C7 C6 0.0 . . . . ?
C3 C7 C6 N1 0.0 . . . . ?
C7 C6 N1 Zn1 -172.6(4) . . . . ?
C7 C6 N1 C5 0.0 . . . . ?
N1 C5 C4 C3 0.0 . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.53427
2 0.46573

_vrf_PLAT111_SIFSIX-24-Zn        
;
PROBLEM: ADDSYM Detects New (Pseudo) Centre of Symmetry .        100 %Fit  
RESPONSE: Precision images were synthesised and examined using APEX III.
Reflection conditions consistent with space group C222(1) were observed, but
were not consistent with Cmcm. Namely, on the h0l plane, reflections with l
index both odd and even were observed.
;
_vrf_PLAT112_SIFSIX-24-Zn        
;
PROBLEM: ADDSYM Detects New (Pseudo) Symm. Elem         m        100 %Fit  
RESPONSE: Precision images were synthesised and examined using APEX III.
Reflection conditions consistent with space group C222(1) were observed, but
were not consistent with Cmcm. Namely, on the h0l plane, reflections with l
index both odd and even were observed.
;
_vrf_PLAT113_SIFSIX-24-Zn        
;
PROBLEM: ADDSYM Suggests Possible Pseudo/New  Space Group       Cmcm Check 
RESPONSE: Precision images were synthesised and examined using APEX III.
Reflection conditions consistent with space group C222(1) were observed, but
were not consistent with Cmcm. Namely, on the h0l plane, reflections with l
index both odd and even were observed.
;
_vrf_PLAT341_SIFSIX-24-Zn        
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.01783 Ang.  
RESPONSE: Due to small crystal size and large void space, high resolution data
could not be obtained. Attempts to grow better crystals have been unsuccesful.
;
# start Validation Reply Form
_vrf_THETM01_SIFSIX-24-Zn        
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: Only small, poorly diffracting crystals could be obtained after many
crystallisation attempts. As a result, high resolution reflections could not be
observed, even with long exposure.
;
