Synthesis of the 3,3'-bipyrrole scaffold from diyne.
Zhang, Wentao; Wang, Luyao; Zhou, Yufeng; Chen, Zhifang; Xiong, Heng-Ying; Zhang, Guangwu; Organic & biomolecular chemistry 23 (2025) 2463–2466; doi:10.1039/d4ob02101k

data_1573823
_publ_section_title
;
 Synthesis of the 3,3'-bipyrrole scaffold from diyne.
;
_journal_issue                   10
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2463
_journal_page_last               2466
_journal_paper_doi               10.1039/d4ob02101k
_journal_volume                  23
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C36 H36 N2'
_chemical_formula_sum            'C36 H36 N2'
_chemical_formula_weight         496.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-10-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-10-31 deposited with the CCDC.	2025-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.543(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.6157(14)
_cell_length_b                   9.4617(5)
_cell_length_c                   11.3780(4)
_cell_measurement_reflns_used    3864
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7470
_cell_measurement_theta_min      3.3583
_cell_volume                     2833.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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   -102.00 -15.00   1.00    2.00    --  -33.50 -57.00 120.00   87
  2  \w    -61.00  23.00   1.00    2.00    --  -33.50  77.00 -90.00   84
  3  \w   -107.00 -65.00   1.00    2.00    --  -33.50 178.00  60.00   42
  4  \w     76.00 103.00   1.00    2.00    --   36.47  57.00 -90.00   27
  5  \w    -25.00  68.00   1.00    2.00    --   36.47 -19.00 -90.00   93
  6  \w     46.00 129.00   1.00    7.50    --  108.00 -30.00 -90.00   83
  7  \w    114.00 176.00   1.00    7.50    --  108.00 111.00-120.00   62
  8  \w     88.00 168.00   1.00    7.50    --  108.00  61.00 -90.00   80
  9  \w    140.00 175.00   1.00    7.50    --  108.00 111.00  30.00   35
 10  \w    126.00 152.00   1.00    7.50    --  108.00 111.00 150.00   26
 11  \w     41.00  93.00   1.00    7.50    --  108.00 -94.00  60.00   52
 12  \w     41.00  82.00   1.00    7.50    --  108.00 -94.00-180.00   41
 13  \w    116.00 142.00   1.00    7.50    --  108.00  76.00-123.00   26
 14  \w    106.00 136.00   1.00    7.50    --  108.00 111.00 -60.00   30
 15  \w     61.00 124.00   1.00    7.50    --  108.00 -45.00 120.00   63
 16  \w     68.00 104.00   1.00    7.50    --  108.00-111.00 -30.00   36
 17  \w    -29.00  21.00   1.00    2.50    --  -33.50  37.00  90.00   50
 18  \w     44.00  76.00   1.00    2.50    --   36.47-131.00  46.00   32
 19  \w     69.00  97.00   1.00    2.50    --   36.47-138.00-128.00   28
 20  \w    -16.00  14.00   1.00    2.50    --   36.47 -77.00-150.00   30
 21  \w     70.00 103.00   1.00    2.50    --   36.47  37.00-120.00   33
 22  \w     51.00  76.00   1.00    2.50    --   36.47 -99.00  30.00   25
 23  \w     11.00  37.00   1.00    2.50    --   36.47 -99.00  30.00   26
 24  \w     70.00  96.00   1.00    2.50    --   36.47 178.00-180.00   26
 25  \w    105.00 130.00   1.00    7.50    --  108.00 111.00 -30.00   25
 26  \w     67.00  93.00   1.00    7.50    --  108.00 -45.00-150.00   26
 27  \w     75.00 109.00   1.00    7.50    --  108.00-111.00-180.00   34
 28  \w     65.00  97.00   1.00    7.50    --  108.00 -94.00  90.00   32
 29  \w    103.00 177.00   1.00    7.50    --  108.00  77.00-150.00   74
 30  \w     81.00 107.00   1.00    7.50    --  108.00-111.00 -90.00   26
 31  \w    127.00 158.00   1.00    7.50    --  108.00  77.00  30.00   31
 32  \w     44.00  70.00   1.00    7.50    --  108.00-111.00-180.00   26
 33  \w    102.00 153.00   1.00    7.50    --  108.00  77.00 120.00   51
 34  \w     56.00 102.00   1.00    7.50    --  108.00-111.00  30.00   46
 35  \w     43.00  95.00   1.00    7.50    --  108.00 -61.00-180.00   52
 36  \w     92.00 145.00   1.00    7.50    --  108.00  30.00-180.00   53
 37  \w    105.00 162.00   1.00    7.50    --  108.00 111.00  90.00   57
 38  \w     69.00  94.00   1.00    2.50    --   36.47-131.00  46.00   25
 39  \w    102.00 128.00   1.00    7.50    --  108.00  77.00  30.00   26
 40  \w     88.00 127.00   1.00    7.50    --  108.00  45.00  90.00   39
 41  \w     74.00 115.00   1.00    7.50    --  108.00 -76.00 109.00   41
 42  \w     96.00 144.00   1.00    7.50    --  108.00  30.00-150.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0082062000
_diffrn_orient_matrix_UB_12      0.1348287000
_diffrn_orient_matrix_UB_13      0.0764852000
_diffrn_orient_matrix_UB_21      0.0579463000
_diffrn_orient_matrix_UB_22      -0.0182781000
_diffrn_orient_matrix_UB_23      0.0087974000
_diffrn_orient_matrix_UB_31      -0.0004916000
_diffrn_orient_matrix_UB_32      0.0895754000
_diffrn_orient_matrix_UB_33      -0.1131793000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0404
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            11618
_diffrn_reflns_point_group_measured_fraction_full 0.869
_diffrn_reflns_point_group_measured_fraction_max 0.855
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.033
_diffrn_reflns_theta_min         3.358
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.509
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90699
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (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    1.164
_exptl_crystal_description       block
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.151
_refine_diff_density_min         -0.153
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1300 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(10)
_refine_ls_extinction_coef       0.00116(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     346
_refine_ls_number_reflns         4681
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0565
_refine_ls_R_factor_gt           0.0478
_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^)+(0.0727P)^2^+0.0781P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1274
_refine_ls_wR_factor_ref         0.1393
_reflns_Friedel_coverage         0.719
_reflns_Friedel_fraction_full    0.737
_reflns_Friedel_fraction_max     0.716
_reflns_number_gt                3993
_reflns_number_total             4681
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob02101k2.cif
_cod_data_source_block           ta4502a
_cod_depositor_comments
'Adding full bibliography for 1573822--1573825.cif.'
_cod_database_code               1573823
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C12H22N1
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.918
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C4(H4A,H4B), C11(H11A,H11B), C19(H19A,H19B), C22(H22A,H22B),
 C29(H29A,H29B)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C24(H24), C25(H25), C27(H27), C28(H28), C31(H31), C32(H32), C33(H33),
  C34(H34), C35(H35)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              91893
_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 1.104
_oxdiff_exptl_absorpt_empirical_full_min 0.911