Vicinal difunctionalization of nitriles: modular construction of N-alkyl amidines and late-stage modification
Xiang, Zixin; Zhang, Simiao; Zhang, Ziyi; Liu, Hang; Wang, Junqi; Chen, Wenwen; Wang, Yong; Wan, Xiaobing; New Journal of Chemistry 48 (2024) 11834–11843; doi:10.1039/D4NJ02051K

data_7063263
_publ_section_title
;
 Vicinal difunctionalization of nitriles: modular construction of N-alkyl
 amidines and late-stage modification
;
_journal_issue                   26
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              11834
_journal_page_last               11843
_journal_paper_doi               10.1039/D4NJ02051K
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety         'C20 H25 Br N2 O2 S'
_chemical_formula_sum            'C20 H25 Br N2 O2 S'
_chemical_formula_weight         437.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_block_doi                 10.5517/ccdc.csd.cc2hjl9y
_audit_creation_date             2023-11-23
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-11-23 deposited with the CCDC.	2024-06-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.570(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8785(8)
_cell_length_b                   11.3457(5)
_cell_length_c                   11.5314(6)
_cell_measurement_reflns_used    5874
_cell_measurement_temperature    223.00(10)
_cell_measurement_theta_max      29.5540
_cell_measurement_theta_min      2.2370
_cell_volume                     2010.61(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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    'XS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      223.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4471
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.931
_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    -62.00  37.00   1.00    2.50    --   12.72 -37.00  90.00   99
  2  \w    -12.00  87.00   1.00    2.50    --   12.72  37.00 -90.00   99
  3  \w     39.00 101.00   1.00    2.50    --   12.72 178.00 120.00   62
  4  \w    -75.00 -25.00   1.00    2.50    --   12.72   0.00-150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0385425000
_diffrn_orient_matrix_UB_12      0.0239398000
_diffrn_orient_matrix_UB_13      0.0109782000
_diffrn_orient_matrix_UB_21      -0.0099916000
_diffrn_orient_matrix_UB_22      0.0270904000
_diffrn_orient_matrix_UB_23      -0.0572750000
_diffrn_orient_matrix_UB_31      -0.0233818000
_diffrn_orient_matrix_UB_32      -0.0509864000
_diffrn_orient_matrix_UB_33      -0.0252504000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0474
_diffrn_reflns_av_unetI/netI     0.0544
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.931
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            17520
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.561
_diffrn_reflns_theta_min         2.231
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.165
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27022
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_description       plate
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.477
_refine_diff_density_min         -0.409
_refine_diff_density_rms         0.067
_refine_ls_extinction_coef       0.0044(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     240
_refine_ls_number_reflns         5243
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.999
_refine_ls_R_factor_all          0.0848
_refine_ls_R_factor_gt           0.0466
_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^)+(0.0481P)^2^+0.6872P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0991
_refine_ls_wR_factor_ref         0.1155
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3471
_reflns_number_total             5243
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj02051k2.cif
_cod_data_source_block           g231102c_auto
_cod_depositor_comments          'Adding full bibliography for 7063263.cif.'
_cod_original_cell_volume        2010.61(17)
_cod_database_code               7063263
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.881
_shelx_estimated_absorpt_t_min   0.478
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), N2(H2), C10(H10), C6(H6), C20(H20), C17(H17), C19(H19), C9(H9),
 C16(H16)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              48904
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.173
_oxdiff_exptl_absorpt_empirical_full_min 0.743