Development of a Scalable Synthesis of trans-4-Fluorocyclohexylamine via Directed Hydrogenation
Leung, Joyce C.; Nguyen, Thach T.; Krawiec, Mariusz; Gao, Donghong A.; Reeves, Jonathan T.; Organic Process Research & Development  (2020) –; doi:10.1021/acs.oprd.0c00444

data_1559548
_publ_section_title
;
 Development of a Scalable Synthesis of trans-4-Fluorocyclohexylamine via
 Directed Hydrogenation
;
_journal_name_full               'Organic Process Research &amp; Development'
_journal_paper_doi               10.1021/acs.oprd.0c00444
_journal_year                    2020
_chemical_formula_moiety         'C13 H15 Br F N O'
_chemical_formula_sum            'C13 H15 Br F N O'
_chemical_formula_weight         300.17
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.2421(11)
_cell_length_b                   5.0967(4)
_cell_length_c                   30.102(2)
_cell_measurement_reflns_used    9850
_cell_measurement_temperature    295(2)
_cell_measurement_theta_max      71.08
_cell_measurement_theta_min      5.64
_cell_volume                     2491.9(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      295.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0491
_diffrn_reflns_av_unetI/netI     0.0454
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            29414
_diffrn_reflns_point_group_measured_fraction_full 0.933
_diffrn_reflns_point_group_measured_fraction_max 0.929
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.610
_diffrn_reflns_theta_min         2.936
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.480
_exptl_absorpt_correction_T_max  0.7535
_exptl_absorpt_correction_T_min  0.3794
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.600
_exptl_crystal_description       needle
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         4.265
_refine_diff_density_min         -2.015
_refine_diff_density_rms         0.196
_refine_ls_abs_structure_details
;
 Flack x determined using 1926 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.447(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     157
_refine_ls_number_reflns         4515
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0764
_refine_ls_R_factor_gt           0.0758
_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^)+(0.0876P)^2^+23.9573P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1923
_refine_ls_wR_factor_ref         0.1928
_reflns_Friedel_coverage         0.826
_reflns_Friedel_fraction_full    0.865
_reflns_Friedel_fraction_max     0.858
_reflns_number_gt                4472
_reflns_number_total             4515
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            op0c00444_si_002.cif
_cod_data_source_block           rdg-adg1-00361a
_cod_database_code               1559548
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.663
_shelx_estimated_absorpt_t_min   0.303
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C12(H12), C9'(H9'), C12'(H12')
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B), C10'(H10C,
 H10D), C11'(H11C,H11D), C13'(H13C,H13D), C14'(H14C,H14D)
2.c Aromatic/amide H refined with riding coordinates:
 N8(H8), C3(H3), C4(H4), C6(H6), C7(H7), N8'(H8'), C3'(H3'), C4'(H4'),
 C6'(H6'), C7'(H7')
;
_olex2_submission_special_instructions 'No special instructions were received'