Visible light-mediated copper catalyzed regioselective diamination of terminal alkynes at room temperature: a facile synthesis of substituted imidazo[1,2-α]pyridines
Charpe, Vaibhav Pramod; Gupta, Mahima; Hwang, Kuo Chu; Green Chemistry 26 (2024) 1329–1337; doi:10.1039/D3GC04062C

data_7247903
_publ_section_title
;
 Visible light-mediated copper catalyzed regioselective diamination of
 terminal alkynes at room temperature: a facile synthesis of substituted
 imidazo[1,2-\a]pyridines
;
_journal_issue                   3
_journal_name_full               'Green Chemistry'
_journal_page_first              1329
_journal_page_last               1337
_journal_paper_doi               10.1039/D3GC04062C
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         'C22 H16 N2'
_chemical_formula_sum            'C22 H16 N2'
_chemical_formula_weight         308.36
_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     dual
_audit_creation_date             2023-08-02
_audit_creation_method
;
Olex2 1.5-ac5-023
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2023-08-07 deposited with the CCDC.	2023-12-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.718(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7695(5)
_cell_length_b                   8.6997(3)
_cell_length_c                   11.0836(3)
_cell_measurement_reflns_used    9209
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      72.6340
_cell_measurement_theta_min      2.6100
_cell_volume                     1616.26(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXD  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.952
_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    -54.00 -26.00   0.50    5.40    --  -14.00 -56.00  -1.19   56
  2  \w    -71.00 -36.00   0.50    5.40    --  -22.00 -49.00  -2.21   70
  3  \w    -78.00 -43.00   0.50    5.40    --  -30.00 -51.00 -30.73   70
  4  \w    -83.00 -48.00   0.50    5.40    --  -34.00 -47.00 -26.45   70
  5  \w    -86.00 -51.00   0.50    5.40    --  -38.00 -51.00 -48.51   70
  6  \w    -90.00 -55.00   0.50    5.40    --  -42.00 -51.00   1.96   70
  7  \w    -90.00 -55.00   0.50    5.40    --  -42.00 -52.00  35.79   70
  8  \w    -92.00 -55.00   0.50    5.40    --  -42.00 -45.00   0.34   74
  9  \w    -94.00 -59.00   0.50    5.40    --  -46.00 -52.00 -54.26   70
 10  \w   -100.00 -62.00   0.50    5.40    --  -50.00 -43.00 160.65   76
 11  \w    -98.00 -63.00   0.50    5.40    --  -50.00 -52.00 -62.88   70
 12  \w   -102.00 -67.00   0.50    5.40    --  -54.00 -51.00 -63.38   70
 13  \w     13.00  64.00   0.50    5.40    --   56.05 -95.00 -60.00  102
 14  \w    -99.00 -73.00   0.50    5.40    --  -58.00 -52.00  -9.41   52
 15  \w    -98.00 -72.00   0.50    5.40    --  -58.00 -52.00 -25.77   52
 16  \w    -96.00 -71.00   0.50    5.40    --  -58.00 -51.00  30.46   50
 17  \w   -100.00 -74.00   0.50    5.40    --  -58.00 -52.00 -34.41   52
 18  \w     71.00  96.00   0.50    5.40    --   58.00  52.00  52.20   50
 19  \w   -103.00 -77.00   0.50    5.40    --  -62.00 -51.00   0.86   52
 20  \w   -103.00 -77.00   0.50    5.40    --  -62.00 -51.00 -30.26   52
 21  \w   -108.00 -81.00   0.50    5.40    --  -66.00 -47.00 -53.00   54
 22  \w   -106.00 -80.00   0.50    5.40    --  -66.00 -51.00  38.54   52
 23  \w   -109.00 -83.00   0.50    5.40    --  -66.00 -52.00 -63.74   52
 24  \w   -106.00 -80.00   0.50    5.40    --  -66.00 -51.00 -37.73   52
 25  \w     59.00  85.00   0.50    5.40    --   69.01  15.00  60.00   52
 26  \w     93.00 119.00   0.50    5.40    --   69.01  15.00  60.00   52
 27  \w   -119.00 -93.00   0.50    5.40    --  -70.00 -49.00-116.15   52
 28  \w   -121.00 -84.00   0.50    5.40    --  -70.00 -34.00-111.94   74
 29  \w   -113.00 -85.00   0.50    5.40    --  -70.00 -48.00 145.47   56
 30  \w   -109.00 -83.00   0.50    5.40    --  -70.00 -43.00  43.28   52
 31  \w   -119.00 -90.00   0.50    5.40    --  -74.00 -58.00 117.97   58
 32  \w   -114.00 -88.00   0.50    5.40    --  -74.00 -40.00  -5.69   52
 33  \w   -113.00 -87.00   0.50    5.40    --  -74.00 -55.00  27.32   52
 34  \w    -89.00 -35.00   0.50    5.40    --  -75.32 111.00  60.00  108
 35  \w    -55.00 -30.00   0.50    5.40    --  -75.32 111.00-180.00   50
 36  \w    -91.00 -60.00   0.50    5.40    --  -75.32 111.00-180.00   62
 37  \w     41.00  67.00   0.50    5.40    --   75.94-111.00  30.00   52
 38  \w     33.00  91.00   0.50    5.40    --   75.94-111.00 -60.00  116
 39  \w     39.00  67.00   0.50    5.40    --   75.94 -95.00  30.00   56
 40  \w   -117.00 -90.00   0.50    5.40    --  -78.00 -58.00 -40.45   54
 41  \w   -118.00 -92.00   0.50    5.40    --  -79.90 -56.00  35.62   52
 42  \w   -121.00 -95.00   0.50    5.40    --  -79.90 -47.00 128.51   52
 43  \w   -125.00-100.00   0.50    5.40    --  -79.90-126.00  45.86   50
 44  \w   -121.00 -95.00   0.50    5.40    --  -79.90 -51.00   3.00   52
 45  \w   -131.00 -92.00   0.50    5.40    --  -79.90 -40.00 150.31   78
 46  \w   -124.00 -98.00   0.50    5.40    --  -79.90 -59.00-164.28   52
 47  \w   -124.00 -91.00   0.50    5.40    --  -79.90-134.00 106.81   66
 48  \w   -123.00 -97.00   0.50    5.40    --  -79.90 -62.00 -44.32   52
 49  \w    -75.00 -33.00   0.50    5.40    --  -79.90 136.00  35.42   84
 50  \w   -120.00 -93.00   0.50    5.40    --  -79.90 -52.00  50.90   54
 51  \w   -124.00 -95.00   0.50    5.40    --  -79.90-119.00  62.42   58
 52  \w   -128.00 -94.00   0.50    5.40    --  -79.90 -52.00 -63.90   68
 53  \w   -118.00 -92.00   0.50    5.40    --  -79.90 -56.00 -35.41   52
 54  \w   -119.00 -92.00   0.50    5.40    --  -79.90 -62.00 138.16   54
 55  \w   -127.00-102.00   0.50    5.40    --  -79.90 -58.00 156.01   50
 56  \w   -129.00 -94.00   0.50    5.40    --  -79.90 -41.00 -30.01   70
 57  \w   -127.00-102.00   0.50    5.40    --  -79.90 -55.00 -84.52   50
 58  \w   -127.00-102.00   0.50    5.40    --  -79.90-122.00-129.03   50
 59  \w     93.00 119.00   0.50    5.40    --   79.90 138.00-124.57   52
 60  \w     94.00 124.00   0.50    5.40    --   79.90  59.00 -18.86   60
 61  \w     46.00  91.00   0.50    5.40    --   83.87 -95.00 120.00   90
 62  \w     40.00  84.00   0.50    5.40    --   83.87-111.00 -90.00   88
 63  \w     45.00  90.00   0.50    5.40    --   83.87 -95.00 -30.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0716294000
_diffrn_orient_matrix_UB_12      -0.0809438000
_diffrn_orient_matrix_UB_13      -0.0562955000
_diffrn_orient_matrix_UB_21      0.0419883000
_diffrn_orient_matrix_UB_22      -0.0096492000
_diffrn_orient_matrix_UB_23      0.1253521000
_diffrn_orient_matrix_UB_31      -0.0394464000
_diffrn_orient_matrix_UB_32      -0.1571377000
_diffrn_orient_matrix_UB_33      0.0213426000
_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  0.0501
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            3602
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.460
_diffrn_reflns_theta_min         2.636
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.578
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86414
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
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    1.267
_exptl_crystal_description       plate
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.162
_refine_diff_density_min         -0.223
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     219
_refine_ls_number_reflns         3602
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0341
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0494P)^2^+0.2088P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0835
_refine_ls_wR_factor_ref         0.0877
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3041
_reflns_number_total             3602
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9878\% 
around [-0.05 0.00 1.00] (reciprocal) or [0.00 -0.00 1.00] (direct)
;
_cod_data_source_file            d3gc04062c2.cif
_cod_data_source_block           230756l3_twin1_hklf4
_cod_depositor_comments
;
Adding full bibliography for 7247899--7247903.cif.

2025-04-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C44 H32 N4'
_cod_original_formula_weight         616.73
_cod_original_formula_moiety         '2(C22 H16 N2)'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        1616.26(8)
_cod_database_code               7247903
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C44 H34 N4'
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.983
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5422(12)
 0.4578(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
3.b Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C)
;
_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 1.181
_oxdiff_exptl_absorpt_empirical_full_min 0.895
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2