# Electronic Supplementary Material (ESI) for ChemComm.
# 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_25
_database_code_depnum_ccdc_archive 'CCDC 2083564'
loop_
_audit_author_name
_audit_author_address
'Stephen Argent'
;University of Nottingham
United Kingdom
;
_audit_update_record             
;
2021-05-13 deposited with the CCDC.	2024-06-02 downloaded from the CCDC.
;
_nottingham_internal_coll_name   ONCRDA
_nottingham_internal_coll_number 18980
_nottingham_internal_coll_client NC/RD
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time '10.00, 40.00'
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczspa
_nottingham_internal_coll_date   17/03/2021
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_NCS_number  ?
_nottingham_internal_process_date 18/03/2021
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 19/03/2021
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 19/03/2021
_nottingham_internal_refinement_user pczspa
_nottingham_internal_self_archive_date ?
_nottingham_internal_self_validation_date ?
_nottingham_internal_self_validation_user ?
_nottingham_internal_validation_date 19/03/2021
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 19/03/2021
_refine_special_details          
;
Ammonium nitrogen atom N8 is disordered across a mirror plane which is coincident with the ring system of the main residue and has hence been placed in part -1 to prevent a bond being between the symmetrically equivalent counterparts.
All hydrogen atoms were observed in the electron density map. Hydrogen atoms on the carbon atoms were geometrically placed and refined with a riding model. The two hydrogen atoms on nitrgoen N8 are refined with the N-H bonds restrained to target values of 0.91 A and their isotropic displacement parameters fixed at 1.2 time Ueq of the nitrogen atom.
;
_audit_creation_date             2021-03-19
_audit_creation_method           
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Cl, C5 H8 F2 N'
_chemical_formula_sum            'C5 H8 Cl F2 N'
_chemical_formula_weight         155.57
_chemical_melting_point          ?
_chemical_oxdiff_formula         C5H8ClF2N
_chemical_oxdiff_usercomment     
'ONCRDA #18980 GVA-1889 NC/RD fomblin micromount'
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'
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'

_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           62
_space_group_name_H-M_alt        'P n m a'
_space_group_name_Hall           '-P 2ac 2n'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z'
'x+1/2, -y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z'
'-x-1/2, y-1/2, z-1/2'

_cell_length_a                   10.0074(7)
_cell_length_b                   7.0673(5)
_cell_length_c                   9.5009(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     671.95(8)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    2188
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      71.9960
_cell_measurement_theta_min      6.4120
_shelx_estimated_absorpt_T_max   0.900
_shelx_estimated_absorpt_T_min   0.400
_exptl_absorpt_coefficient_mu    4.681
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.569
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.538
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             320
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-5 -1 0 0.0116
5 1 0 0.0116
0 -1 0 0.0171
0 1 0 0.0171
0 0 -1 0.1297
0 -3 4 0.0881

_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.023
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
-4.9897 -1.0241 0.0033 -0.1859 0.7594 -0.0809
4.9897 1.0241 -0.0033 0.1859 -0.7594 0.0809
0.0042 -0.9996 -0.0010 -0.1546 -0.0081 -0.0481
-0.0042 0.9996 0.0010 0.1546 0.0081 0.0481
-0.0026 -0.0008 -0.9990 0.0647 -0.0063 -0.2078
0.0228 -2.9955 3.9928 -0.7225 0.0009 0.6867

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0526
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            4429
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.630
_diffrn_reflns_theta_min         6.424
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     -5.00  35.00   1.00   10.00    --  -42.12  19.00 -60.00   40
  2  ω   -114.00 -18.00   1.00   10.00    --  -42.12 -38.00 120.00   96
  3  ω    -28.00  68.00   1.00   10.00    --   42.12 -57.00 -90.00   96
  4  ω     27.00 127.00   1.00   40.00    --  101.44 -77.00 150.00  100
  5  ω     28.00  57.00   1.00   40.00    --  101.44 -30.00  60.00   29
  6  ω     28.00  57.00   1.00   40.00    --  101.44 -30.00 120.00   29
  7  ω     28.00  57.00   1.00   40.00    --  101.44 -30.00  90.00   29
  8  ω     28.00  57.00   1.00   40.00    --  101.44 -30.00-120.00   29
  9  ω     31.00  72.00   1.00   40.00    --  101.44 -45.00 150.00   41
 10  ω     31.00  72.00   1.00   40.00    --  101.44 -45.00-180.00   41
 11  ω     22.00 178.00   1.00   40.00    --  101.44   0.00  90.00  156
 12  ω     -8.00  34.00   1.00   10.00    --  -42.12  23.00  74.00   42
 13  ω     17.00 112.00   1.00   10.00    --   42.12  57.00 -60.00   95
 14  ω     17.00 112.00   1.00   10.00    --   42.12  57.00  30.00   95
 15  ω     28.00  57.00   1.00   40.00    --  101.44 -30.00 -90.00   29
 16  ω     28.00  57.00   1.00   40.00    --  101.44 -30.00 -60.00   29
 17  ω     75.00 123.00   1.00   40.00    --  101.44  30.00-120.00   48
 18  ω     97.00 175.00   1.00   40.00    --  101.44 125.00-180.00   78
;
_diffrn_measurement_device       'κ-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan S2'
_diffrn_measurement_method       'ω scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0054517000
_diffrn_orient_matrix_UB_12      0.1547750000
_diffrn_orient_matrix_UB_13      -0.0648642000
_diffrn_orient_matrix_UB_21      -0.1537207000
_diffrn_orient_matrix_UB_22      0.0074468000
_diffrn_orient_matrix_UB_23      0.0066840000
_diffrn_orient_matrix_UB_31      0.0065101000
_diffrn_orient_matrix_UB_32      0.0479301000
_diffrn_orient_matrix_UB_33      0.2079175000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                675
_reflns_number_total             714
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         0.336
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.055
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     61
_refine_ls_number_reflns         714
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0318
_refine_ls_restrained_S_all      1.083
_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)+(0.0411P)²+0.2736P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0811
_refine_ls_wR_factor_ref         0.0819
_olex2_refinement_description    
;
1. Restrained distances
 N8-H8B = N8-H8A
 0.91 with sigma of 0.02
2. Others
 Fixed Sof: H7A(0.5) H7B(0.5) N8(0.5) H8A(0.5) H8B(0.5) H9A(0.5) H9B(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C9(H9A,H9B)
3.b X=CH2 refined with riding coordinates:
 C2(H2A,H2B)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
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
Cl1 Cl 0.15976(5) 0.750000 0.45211(6) 0.0245(2) Uani 1 2 d S T P . .
C2 C 0.4584(3) 0.250000 0.5812(3) 0.0302(6) Uani 1 2 d S T P . .
H2A H 0.542633 0.250000 0.535067 0.036 Uiso 1 2 calc R U P . .
H2B H 0.454297 0.250000 0.681139 0.036 Uiso 1 2 calc R U P . .
C3 C 0.3465(2) 0.250000 0.5061(3) 0.0234(5) Uani 1 2 d S T P B .
C4 C 0.3410(2) 0.250000 0.3485(2) 0.0235(5) Uani 1 2 d S T P B .
F6 F 0.40593(10) 0.40310(15) 0.29145(10) 0.0286(3) Uani 1 1 d . . . . .
C7 C 0.1946(3) 0.250000 0.3087(3) 0.0285(5) Uani 1 2 d S T P . .
H7A H 0.177588 0.335644 0.228210 0.034 Uiso 0.5 1 calc R U P A -1
H7B H 0.163926 0.121035 0.283947 0.034 Uiso 0.5 1 calc R U P A -1
N8 N 0.1284(3) 0.3179(4) 0.4354(3) 0.0235(6) Uani 0.5 1 d D . P B -1
H8A H 0.041(2) 0.294(6) 0.446(3) 0.028 Uiso 0.5 1 d D U P C -1
H8B H 0.136(4) 0.450(3) 0.436(4) 0.028 Uiso 0.5 1 d D U P D -1
C9 C 0.2056(3) 0.250000 0.5601(2) 0.0248(5) Uani 1 2 d S T P . .
H9A H 0.177190 0.121366 0.588504 0.030 Uiso 0.5 1 calc R U P B -1
H9B H 0.195332 0.336980 0.641061 0.030 Uiso 0.5 1 calc R U P B -1


_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
C2 H2A 0.9500 . ?
C2 H2B 0.9500 . ?
C2 C3 1.328(4) . ?
C3 C4 1.499(3) . ?
C3 C9 1.500(3) . ?
C4 F6 1.3738(17) 7_565 ?
C4 F6 1.3738(17) . ?
C4 C7 1.513(3) . ?
C7 H7A 0.9900 . ?
C7 H7B 0.9900 . ?
C7 N8 1.455(4) . ?
N8 H8A 0.897(18) . ?
N8 H8B 0.933(19) . ?
N8 C9 1.493(4) . ?
C9 H9A 0.9900 . ?
C9 H9B 0.9900 . ?

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
H2A C2 H2B 120.0 . . ?
C3 C2 H2A 120.0 . . ?
C3 C2 H2B 120.0 . . ?
C2 C3 C4 124.6(2) . . ?
C2 C3 C9 127.5(2) . . ?
C4 C3 C9 107.86(19) . . ?
C3 C4 C7 106.60(19) . . ?
F6 C4 C3 112.14(13) 7_565 . ?
F6 C4 C3 112.14(13) . . ?
F6 C4 F6 103.92(17) 7_565 . ?
F6 C4 C7 111.07(13) . . ?
F6 C4 C7 111.07(13) 7_565 . ?
C4 C7 H7A 111.1 . . ?
C4 C7 H7B 111.1 . . ?
H7A C7 H7B 109.0 . . ?
N8 C7 C4 103.5(2) . . ?
N8 C7 H7A 111.1 . . ?
N8 C7 H7B 111.1 . . ?
C7 N8 H8A 118(2) . . ?
C7 N8 H8B 107(3) . . ?
C7 N8 C9 108.4(2) . . ?
H8A N8 H8B 106(4) . . ?
C9 N8 H8A 111(2) . . ?
C9 N8 H8B 106(3) . . ?
C3 C9 H9A 111.3 . . ?
C3 C9 H9B 111.3 . . ?
N8 C9 C3 102.41(19) . . ?
N8 C9 H9A 111.3 . . ?
N8 C9 H9B 111.3 . . ?
H9A C9 H9B 109.2 . . ?

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
_geom_hbond_publ_flag
N8 H8A Cl1 0.897(18) 2.25(2) 3.113(3) 161(3) 3_546 yes
N8 H8B Cl1 0.933(19) 2.14(2) 3.074(3) 176(4) . yes

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
C2 C3 C4 F6 58.24(13) . . . 7_565 ?
C2 C3 C4 F6 -58.24(13) . . . . ?
C2 C3 C4 C7 180.000(0) . . . . ?
C2 C3 C9 N8 160.78(12) . . . . ?
C3 C4 C7 N8 19.83(12) . . . . ?
C4 C3 C9 N8 -19.22(12) . . . . ?
C4 C7 N8 C9 -33.2(2) . . . . ?
F6 C4 C7 N8 -102.60(19) . . . . ?
F6 C4 C7 N8 142.26(16) 7_565 . . . ?
C7 N8 C9 C3 33.0(2) . . . . ?
C9 C3 C4 F6 121.76(13) . . . . ?
C9 C3 C4 F6 -121.76(13) . . . 7_565 ?
C9 C3 C4 C7 0.000(0) . . . . ?

_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_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 1.239
_oxdiff_exptl_absorpt_empirical_full_min 0.758
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: isopropanol, hexane'
