# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# 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_ean223
_database_code_depnum_ccdc_archive 'CCDC 2045499'
loop_
_audit_author_name
_audit_author_address
'Jeff W. Kampf'
;University of Michigan
United States of America
;
_audit_update_record             
;
2020-11-20 deposited with the CCDC.	2022-05-11 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H13 F2 N O'
_chemical_formula_sum            'C12 H13 F2 N O'
_chemical_formula_weight         225.23

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'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_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+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   7.32492(6)
_cell_length_b                   7.77679(5)
_cell_length_c                   18.64270(13)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1061.969(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    85(2)
_cell_measurement_reflns_used    13269
_cell_measurement_theta_min      4.7230
_cell_measurement_theta_max      69.3430

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.409
_exptl_crystal_F_000             472
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    0.964
_shelx_estimated_absorpt_T_min   0.861
_shelx_estimated_absorpt_T_max   0.910
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.93266
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
; 
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019) 
Empirical absorption correction using spherical harmonics, 
 implemented in SCALE3 ABSPACK scaling algorithm. 
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      85(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'micro-focus rotating anode'
_diffrn_measurement_device_type  'Rigaku Saturn 944+ CCD'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16093
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_av_R_equivalents  0.0574
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         4.744
_diffrn_reflns_theta_max         69.368
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             1976
_reflns_number_gt                1969
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.677
_reflns_Friedel_fraction_max     0.986
_reflns_Friedel_fraction_full    1.000

_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       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_structure_solution    'SHELXT (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0433P)²+0.1608P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual-space
_atom_sites_solution_secondary   ?difmap
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_extinction_coef       0.0066(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 
; 
 Flack x determined using 790 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 

 While the Flack and Hooft statistics are somewhat ambigious, the
 Biovet analysis via PLATON is more definitive.

Bayesian Statistics
Student_T Nu       76
Select Pairs      798
Theta_Min ..     8.65
Theta_Max ..    69.21
P2(true)....    1.000
P3(true)....    1.000
P3(rac-twin)  0.3E-03
P3(false) ..  0.1E-61
G ..........   0.5645
G (su) .....   0.0886
Hooft y ....  0.22(4)

;
_refine_ls_abs_structure_Flack   0.23(5)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         1976
_refine_ls_number_parameters     151
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0271
_refine_ls_R_factor_gt           0.0269
_refine_ls_wR_factor_ref         0.0699
_refine_ls_wR_factor_gt          0.0698
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_restrained_S_all      1.074
_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_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 0.3106(2) 0.69078(18) 0.58436(7) 0.0167(3) Uani 1 1 d . . . . .
H1N H 0.415(4) 0.682(3) 0.5612(13) 0.032(6) Uiso 1 1 d . . . . .
O1 O 0.14734(15) 0.79900(15) 0.49030(6) 0.0201(3) Uani 1 1 d . . . . .
F1 F 0.67475(13) 0.51846(12) 0.67658(5) 0.0230(3) Uani 1 1 d . . . . .
F2 F 0.17998(13) 0.17753(13) 0.60063(5) 0.0237(3) Uani 1 1 d . . . . .
C1 C 0.1612(2) 0.75963(19) 0.55421(8) 0.0153(3) Uani 1 1 d . . . . .
C2 C 0.0161(2) 0.7799(2) 0.61122(8) 0.0185(4) Uani 1 1 d . . . . .
H2A H -0.078366 0.689509 0.606741 0.022 Uiso 1 1 calc R U . . .
H2B H -0.043117 0.894075 0.607927 0.022 Uiso 1 1 calc R U . . .
C3 C 0.1216(2) 0.7614(2) 0.68178(8) 0.0190(4) Uani 1 1 d . . . . .
H3A H 0.049107 0.696427 0.717460 0.023 Uiso 1 1 calc R U . . .
H3B H 0.151707 0.875734 0.701949 0.023 Uiso 1 1 calc R U . . .
C4 C 0.2974(2) 0.6622(2) 0.66171(8) 0.0160(3) Uani 1 1 d . . . . .
H4 H 0.404886 0.715120 0.686366 0.019 Uiso 1 1 calc R U . . .
C5 C 0.2847(2) 0.4691(2) 0.68123(9) 0.0170(4) Uani 1 1 d . . . . .
H5 H 0.158881 0.429311 0.668636 0.020 Uiso 1 1 calc R U . . .
C6 C 0.3084(2) 0.4465(2) 0.76228(9) 0.0200(4) Uani 1 1 d . . . . .
H6A H 0.295677 0.324669 0.774703 0.030 Uiso 1 1 calc R U . . .
H6B H 0.214941 0.513404 0.787511 0.030 Uiso 1 1 calc R U . . .
H6C H 0.429805 0.487050 0.776517 0.030 Uiso 1 1 calc R U . . .
C7 C 0.4190(2) 0.3580(2) 0.63979(8) 0.0159(3) Uani 1 1 d . . . . .
C8 C 0.6061(2) 0.3848(2) 0.63772(8) 0.0174(4) Uani 1 1 d . . . . .
C9 C 0.7275(2) 0.2859(2) 0.59937(9) 0.0203(4) Uani 1 1 d . . . . .
H9 H 0.854364 0.311258 0.599905 0.024 Uiso 1 1 calc R U . . .
C10 C 0.6607(3) 0.1483(2) 0.55989(8) 0.0207(4) Uani 1 1 d . . . . .
H10 H 0.742045 0.079070 0.532674 0.025 Uiso 1 1 calc R U . . .
C11 C 0.4753(3) 0.1115(2) 0.56009(9) 0.0197(4) Uani 1 1 d . . . . .
H11 H 0.427758 0.017401 0.533521 0.024 Uiso 1 1 calc R U . . .
C12 C 0.3621(2) 0.2164(2) 0.60022(8) 0.0176(3) 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
N1 C1 1.342(2) . ?
N1 C4 1.462(2) . ?
N1 H1N 0.88(3) . ?
O1 C1 1.2344(19) . ?
F1 C8 1.3631(18) . ?
F2 C12 1.368(2) . ?
C1 C2 1.511(2) . ?
C2 C3 1.532(2) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 C4 1.547(2) . ?
C3 H3A 0.9900 . ?
C3 H3B 0.9900 . ?
C4 C5 1.548(2) . ?
C4 H4 1.0000 . ?
C5 C7 1.520(2) . ?
C5 C6 1.531(2) . ?
C5 H5 1.0000 . ?
C6 H6A 0.9800 . ?
C6 H6B 0.9800 . ?
C6 H6C 0.9800 . ?
C7 C8 1.387(2) . ?
C7 C12 1.390(2) . ?
C8 C9 1.376(2) . ?
C9 C10 1.388(2) . ?
C9 H9 0.9500 . ?
C10 C11 1.387(3) . ?
C10 H10 0.9500 . ?
C11 C12 1.383(2) . ?
C11 H11 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
_geom_angle_publ_flag
C1 N1 C4 114.83(13) . . ?
C1 N1 H1N 122.1(16) . . ?
C4 N1 H1N 122.0(16) . . ?
O1 C1 N1 124.77(15) . . ?
O1 C1 C2 126.52(15) . . ?
N1 C1 C2 108.71(13) . . ?
C1 C2 C3 103.84(13) . . ?
C1 C2 H2A 111.0 . . ?
C3 C2 H2A 111.0 . . ?
C1 C2 H2B 111.0 . . ?
C3 C2 H2B 111.0 . . ?
H2A C2 H2B 109.0 . . ?
C2 C3 C4 105.01(12) . . ?
C2 C3 H3A 110.7 . . ?
C4 C3 H3A 110.7 . . ?
C2 C3 H3B 110.7 . . ?
C4 C3 H3B 110.7 . . ?
H3A C3 H3B 108.8 . . ?
N1 C4 C3 102.56(12) . . ?
N1 C4 C5 112.54(13) . . ?
C3 C4 C5 112.13(13) . . ?
N1 C4 H4 109.8 . . ?
C3 C4 H4 109.8 . . ?
C5 C4 H4 109.8 . . ?
C7 C5 C6 111.27(13) . . ?
C7 C5 C4 113.13(13) . . ?
C6 C5 C4 109.66(13) . . ?
C7 C5 H5 107.5 . . ?
C6 C5 H5 107.5 . . ?
C4 C5 H5 107.5 . . ?
C5 C6 H6A 109.5 . . ?
C5 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
C5 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
C8 C7 C12 113.60(14) . . ?
C8 C7 C5 124.64(14) . . ?
C12 C7 C5 121.76(15) . . ?
F1 C8 C9 117.64(15) . . ?
F1 C8 C7 117.66(14) . . ?
C9 C8 C7 124.70(15) . . ?
C8 C9 C10 118.59(16) . . ?
C8 C9 H9 120.7 . . ?
C10 C9 H9 120.7 . . ?
C11 C10 C9 120.17(16) . . ?
C11 C10 H10 119.9 . . ?
C9 C10 H10 119.9 . . ?
C12 C11 C10 117.82(16) . . ?
C12 C11 H11 121.1 . . ?
C10 C11 H11 121.1 . . ?
F2 C12 C11 117.23(15) . . ?
F2 C12 C7 117.68(14) . . ?
C11 C12 C7 125.09(16) . . ?

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
C4 N1 C1 O1 177.37(15) . . . . ?
C4 N1 C1 C2 -2.63(18) . . . . ?
O1 C1 C2 C3 -164.23(15) . . . . ?
N1 C1 C2 C3 15.77(16) . . . . ?
C1 C2 C3 C4 -22.03(16) . . . . ?
C1 N1 C4 C3 -11.51(17) . . . . ?
C1 N1 C4 C5 109.18(15) . . . . ?
C2 C3 C4 N1 20.36(16) . . . . ?
C2 C3 C4 C5 -100.61(14) . . . . ?
N1 C4 C5 C7 44.29(18) . . . . ?
C3 C4 C5 C7 159.31(13) . . . . ?
N1 C4 C5 C6 169.15(13) . . . . ?
C3 C4 C5 C6 -75.83(16) . . . . ?
C6 C5 C7 C8 -69.1(2) . . . . ?
C4 C5 C7 C8 54.9(2) . . . . ?
C6 C5 C7 C12 110.38(16) . . . . ?
C4 C5 C7 C12 -125.63(15) . . . . ?
C12 C7 C8 F1 -178.33(13) . . . . ?
C5 C7 C8 F1 1.2(2) . . . . ?
C12 C7 C8 C9 1.5(2) . . . . ?
C5 C7 C8 C9 -178.98(15) . . . . ?
F1 C8 C9 C10 179.47(13) . . . . ?
C7 C8 C9 C10 -0.4(2) . . . . ?
C8 C9 C10 C11 -0.6(2) . . . . ?
C9 C10 C11 C12 0.3(2) . . . . ?
C10 C11 C12 F2 -179.24(14) . . . . ?
C10 C11 C12 C7 1.0(2) . . . . ?
C8 C7 C12 F2 178.40(14) . . . . ?
C5 C7 C12 F2 -1.1(2) . . . . ?
C8 C7 C12 C11 -1.8(2) . . . . ?
C5 C7 C12 C11 178.63(15) . . . . ?

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
N1 H1N O1 0.88(3) 1.96(3) 2.8333(18) 171(3) 4_566 yes

_refine_diff_density_max         0.169
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.048


_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
