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_1573824
_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_formula_moiety         'C46 H36 N2'
_chemical_formula_sum            'C46 H36 N2'
_chemical_formula_weight         616.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-10-30
_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                 109.461(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.6526(4)
_cell_length_b                   5.85340(10)
_cell_length_c                   18.1057(5)
_cell_measurement_reflns_used    4074
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.1840
_cell_measurement_theta_min      4.3970
_cell_volume                     1664.01(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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   -108.00 -36.00   0.60    2.00    --  -33.50 178.00 -30.00  120
  2  \w    -92.00 -50.00   0.60    2.00    --  -33.50 178.00-120.00   70
  3  \w    -98.00 -15.80   0.60    2.00    --  -33.50 -57.00  60.00  137
  4  \w    -65.00 -20.60   0.60    2.00    --  -33.50 -57.00 -30.00   74
  5  \w    -46.00  -7.60   0.60    2.00    --  -33.50  19.00 120.00   64
  6  \w     37.00  63.40   0.60    2.00    --   36.47  19.00 -30.00   44
  7  \w      2.00  66.80   0.60    2.00    --   36.47 -99.00-180.00  108
  8  \w     61.00  86.20   0.60    2.00    --   36.47 178.00 -90.00   42
  9  \w     61.00 103.60   0.60    2.00    --   36.47 178.00-120.00   71
 10  \w     19.00  70.60   0.60    2.00    --   36.47  57.00 -60.00   86
 11  \w     18.00  77.40   0.60    2.00    --   36.47  57.00 -30.00   99
 12  \w    -17.00  49.00   0.60    2.00    --   36.47 -77.00 -90.00  110
 13  \w    -18.00  30.00   0.60    2.00    --   36.47 -77.00-120.00   80
 14  \w     66.00 107.40   0.60    2.00    --   36.47 178.00  90.00   69
 15  \w      3.00  32.40   0.60    2.00    --   36.47  19.00 -30.00   49
 16  \w     38.00  74.60   0.60    2.00    --   36.47 -99.00 -90.00   61
 17  \w     26.00  52.40   0.60    2.00    --   36.47 -99.00-150.00   44
 18  \w     44.80 109.00   0.60   14.00    --  108.00-111.00-180.00  107
 19  \w     39.00  72.60   0.60   14.00    --  108.00 -94.00-150.00   56
 20  \w    119.00 167.60   0.60   14.00    --  108.00  77.00 -60.00   81
 21  \w     43.00 178.00   0.60   14.00    --  108.00   0.00 -60.00  225
 22  \w    107.00 136.40   0.60   14.00    --  108.00 111.00  90.00   49
 23  \w     66.00 101.40   0.60   14.00    --  108.00 -95.00  75.00   59
 24  \w     47.00 101.00   0.60   14.00    --  108.00 -94.00-120.00   90
 25  \w    134.00 173.60   0.60   14.00    --  108.00  61.00   0.00   66
 26  \w     82.00 176.20   0.60   14.00    --  108.00  30.00 150.00  157
 27  \w     48.00  90.60   0.60   14.00    --  108.00 -94.00  30.00   71
 28  \w     76.60 109.00   0.60   14.00    --  108.00-111.00 -30.00   54
 29  \w    115.00 163.00   0.60   14.00    --  108.00 111.00-120.00   80
 30  \w    106.00 132.40   0.60   14.00    --  108.00 111.00-150.00   44
 31  \w     95.00 169.40   0.60   14.00    --  108.00  61.00 -30.00  124
 32  \w     41.00 118.40   0.60   14.00    --  108.00 -45.00 -30.00  129
 33  \w    141.00 176.40   0.60   14.00    --  108.00  77.00 120.00   59
 34  \w    147.00 173.40   0.60   14.00    --  108.00  61.00 -90.00   44
;
_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      -0.0447132000
_diffrn_orient_matrix_UB_12      -0.1661743000
_diffrn_orient_matrix_UB_13      0.0396872000
_diffrn_orient_matrix_UB_21      -0.0680404000
_diffrn_orient_matrix_UB_22      0.1825785000
_diffrn_orient_matrix_UB_23      -0.0043417000
_diffrn_orient_matrix_UB_31      -0.0547159000
_diffrn_orient_matrix_UB_32      -0.0911769000
_diffrn_orient_matrix_UB_33      -0.0809616000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0309
_diffrn_reflns_av_unetI/netI     0.0275
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_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       17
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            10833
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.069
_diffrn_reflns_theta_max         67.069
_diffrn_reflns_theta_min         4.416
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.541
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92653
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.231
_exptl_crystal_description       block
_exptl_crystal_F_000             652
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.335
_refine_diff_density_min         -0.259
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     224
_refine_ls_number_reflns         2950
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0691
_refine_ls_R_factor_gt           0.0606
_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^)+(0.1115P)^2^+0.4206P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1793
_refine_ls_wR_factor_ref         0.1901
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2455
_reflns_number_total             2950
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ob02101k2.cif
_cod_data_source_block           t4461
_cod_depositor_comments
'Adding full bibliography for 1573822--1573825.cif.'
_cod_database_code               1573824
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C12H22O5N1
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.918
_reflns_odcompleteness_completeness 99.88
_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
2. Uiso/Uaniso restraints and constraints
Uanis(C22A) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(C19A) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C23A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19) = Uanis(C19A)
Uanis(C20) = Uanis(C20A)
Uanis(C23) = Uanis(C23A)
Uanis(C22) = Uanis(C22A)
Uanis(C21) = Uanis(C21A)
Uanis(C18) = Uanis(C18A)
3. Others
 Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=
 Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=1-FVAR(1)
 Sof(C23)=Sof(H23)=Sof(C22)=Sof(H22)=Sof(C21)=Sof(H21)=Sof(C20)=Sof(H20)=
 Sof(C19)=Sof(H19)=Sof(C18)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14),
 C15(H15), C16(H16), C17(H17), C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A),
 C23(H23), C22(H22), C21(H21), C20(H20), C19(H19), C23A(H23A)
4.c Fitted hexagon refined as free rotating group:
 C23(C22,C21,C20,C19,C18)
;
_shelx_res_checksum              50736
_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 1.870
_oxdiff_exptl_absorpt_empirical_full_min 0.864