Modular synthesis of cyclic β-difluoroamines.
Charlesworth, Natalie G.; Arunprasath, Dhanarajan; Graham, Mark A.; Argent, Stephen P.; Datsenko, Oleksandr P.; Mykhailiuk, Pavel K.; Denton, Ross M.; Chemical communications (Cambridge, England) 60 (2024) 7701–7704; doi:10.1039/d4cc00640b

data_7133176
_publ_section_title
;
 Modular synthesis of cyclic &#x3b2;-difluoroamines.
;
_journal_issue                   60
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              7701
_journal_page_last               7704
_journal_paper_doi               10.1039/d4cc00640b
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'Cl, C5 H8 F2 N'
_chemical_formula_sum            'C5 H8 Cl F2 N'
_chemical_formula_weight         155.57
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-03-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-05-13 deposited with the CCDC.	2024-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.0074(7)
_cell_length_b                   7.0673(5)
_cell_length_c                   9.5009(6)
_cell_measurement_reflns_used    2188
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      71.9960
_cell_measurement_theta_min      6.4120
_cell_volume                     671.95(8)
_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)'
_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  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -5.00  35.00   1.00   10.00    --  -42.12  19.00 -60.00   40
  2  \w   -114.00 -18.00   1.00   10.00    --  -42.12 -38.00 120.00   96
  3  \w    -28.00  68.00   1.00   10.00    --   42.12 -57.00 -90.00   96
  4  \w     27.00 127.00   1.00   40.00    --  101.44 -77.00 150.00  100
  5  \w     28.00  57.00   1.00   40.00    --  101.44 -30.00  60.00   29
  6  \w     28.00  57.00   1.00   40.00    --  101.44 -30.00 120.00   29
  7  \w     28.00  57.00   1.00   40.00    --  101.44 -30.00  90.00   29
  8  \w     28.00  57.00   1.00   40.00    --  101.44 -30.00-120.00   29
  9  \w     31.00  72.00   1.00   40.00    --  101.44 -45.00 150.00   41
 10  \w     31.00  72.00   1.00   40.00    --  101.44 -45.00-180.00   41
 11  \w     22.00 178.00   1.00   40.00    --  101.44   0.00  90.00  156
 12  \w     -8.00  34.00   1.00   10.00    --  -42.12  23.00  74.00   42
 13  \w     17.00 112.00   1.00   10.00    --   42.12  57.00 -60.00   95
 14  \w     17.00 112.00   1.00   10.00    --   42.12  57.00  30.00   95
 15  \w     28.00  57.00   1.00   40.00    --  101.44 -30.00 -90.00   29
 16  \w     28.00  57.00   1.00   40.00    --  101.44 -30.00 -60.00   29
 17  \w     75.00 123.00   1.00   40.00    --  101.44  30.00-120.00   48
 18  \w     97.00 175.00   1.00   40.00    --  101.44 125.00-180.00   78
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan S2'
_diffrn_measurement_method       '\w 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_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_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_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_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.538
_exptl_crystal_description       needle
_exptl_crystal_F_000             320
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: isopropanol, hexane'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.023
_refine_diff_density_max         0.336
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.055
_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_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0318
_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/[\s^2^(Fo^2^)+(0.0411P)^2^+0.2736P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0811
_refine_ls_wR_factor_ref         0.0819
_reflns_Friedel_coverage         0.000
_reflns_number_gt                675
_reflns_number_total             714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00640b2.cif
_cod_data_source_block           25
_cod_depositor_comments          'Adding full bibliography for 7133176.cif.'
_cod_database_code               7133176
_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_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_validation_date 19/03/2021
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 19/03/2021
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C5H8ClF2N
_chemical_oxdiff_usercomment
'ONCRDA #18980 GVA-1889 NC/RD fomblin micromount'
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.400
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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)
;
_shelx_res_checksum              94892
_shelx_hkl_checksum              61828
_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