Stereo effects for efficient synthesis of orange-red multiple resonance emitters centered on a pyridine ring.
Du, Mingxu; Mai, Minqiang; Zhang, Dongdong; Duan, Lian; Zhang, Yuewei; Chemical science 15 (2024) 3148–3154; doi:10.1039/d3sc06470k

data_1570793
_publ_section_title
;
 Stereo effects for efficient synthesis of orange-red multiple resonance
 emitters centered on a pyridine ring.
;
_journal_issue                   9
_journal_name_full               'Chemical science'
_journal_page_first              3148
_journal_page_last               3154
_journal_paper_doi               10.1039/d3sc06470k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C85 H94 B N5'
_chemical_formula_sum            'C85 H94 B N5'
_chemical_formula_weight         1196.46
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-17
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-09-23 deposited with the CCDC.	2024-01-17 downloaded from the CCDC.
;
_cell_angle_alpha                89.702(2)
_cell_angle_beta                 77.628(2)
_cell_angle_gamma                79.792(2)
_cell_formula_units_Z            2
_cell_length_a                   13.9175(4)
_cell_length_b                   14.8192(4)
_cell_length_c                   19.2412(5)
_cell_measurement_reflns_used    37439
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.0310
_cell_measurement_theta_min      2.2790
_cell_volume                     3812.69(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.963
_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   -116.00 -33.00   0.50    1.41    --  -48.14 -60.00  41.00  166
  2  \w    -63.00  17.00   0.50    1.41    --  -48.14  60.00-178.00  160
  3  \w    -22.00   6.00   0.50    1.41    --   48.14 -60.00  41.00   56
  4  \w     34.00 117.00   0.50    1.41    --   48.14  60.00-178.00  166
  5  \w   -152.00 -98.00   0.50    7.00    -- -104.00 -60.00  41.00  108
  6  \w    -67.00 -36.00   0.50    7.00    -- -104.00  60.00-178.00   62
  7  \w     35.00  60.00   0.50    7.00    --  106.93 -60.00  41.00   50
  8  \w     94.00 174.00   0.50    7.00    --  106.93  60.00-178.00  160
  9  \w   -107.00 -77.00   0.50    1.41    --  -48.14-125.00-180.00   60
 10  \w   -115.00 -89.00   0.50    1.41    --  -48.14-125.00  90.00   52
 11  \w    -20.00  26.00   0.50    1.41    --   48.14 -19.00  90.00   92
 12  \w     -6.00  28.00   0.50    1.41    --   48.14 -19.00-150.00   68
 13  \w     13.00  57.00   0.50    1.41    --   48.14 -60.00  41.00   88
 14  \w     25.00  95.00   0.50    1.41    --   48.14-125.00  60.00  140
 15  \w   -157.00 -94.00   0.50    7.00    -- -104.00 -19.00-120.00  126
 16  \w   -175.00 -94.00   0.50    7.00    -- -104.00 -19.00 -30.00  162
 17  \w   -175.00-114.00   0.50    7.00    -- -104.00 -19.00 -90.00  122
 18  \w    -64.00 -39.00   0.50    7.00    -- -104.00  57.00  90.00   50
 19  \w   -125.00 -48.00   0.50    7.00    -- -104.00 143.00 174.62  154
 20  \w    -63.00 -32.00   0.50    7.00    -- -104.00  57.00 -30.00   62
 21  \w    -63.00 -36.00   0.50    7.00    -- -104.00  57.00   0.00   54
 22  \w    -64.00 -39.00   0.50    7.00    -- -104.00  57.00-150.00   50
 23  \w   -159.00-133.00   0.50    7.00    -- -104.00 -99.00 150.00   52
 24  \w   -108.00 -77.00   0.50    7.00    -- -104.00 109.00 126.44   62
 25  \w   -113.00 -87.00   0.50    7.00    -- -104.00 -99.00 150.00   52
 26  \w     96.00 177.00   0.50    7.00    --  106.93  19.00 120.00  162
 27  \w     39.00  98.00   0.50    7.00    --  106.93 -99.00   0.00  118
 28  \w     39.00 106.00   0.50    7.00    --  106.93 -99.00 -60.00  134
 29  \w     46.00  98.00   0.50    7.00    --  106.93 -99.00 -30.00  104
 30  \w     37.00  84.00   0.50    7.00    --  106.93-125.00 120.00   94
 31  \w     35.00 101.00   0.50    7.00    --  106.93 -99.00 150.00  132
 32  \w    107.00 143.00   0.50    7.00    --  106.93  19.00-180.00   72
 33  \w     43.00  94.00   0.50    7.00    --  106.93 -99.00-180.00  102
 34  \w     38.00 105.00   0.50    7.00    --  106.93 -99.00  30.00  134
 35  \w     81.00 106.00   0.50    7.00    --  106.93 -99.00-120.00   50
 36  \w     59.00 105.00   0.50    7.00    --  106.93 -99.00  60.00   92
 37  \w     36.00  68.00   0.50    7.00    --  106.93 -99.00 120.00   64
 38  \w     37.00  76.00   0.50    7.00    --  106.93 -99.00-120.00   78
 39  \w     54.00  89.00   0.50    7.00    --  106.93 -99.00 -90.00   70
 40  \w     55.00 111.00   0.50    7.00    --  106.93-125.00 150.00  112
 41  \w     43.00  68.00   0.50    7.00    --  106.93 -57.00-150.00   50
 42  \w     38.00  63.00   0.50    7.00    --  106.93 -57.00-180.00   50
 43  \w   -154.00-128.00   0.50   16.00    -- -104.00 -60.00  41.00   52
 44  \w   -108.00 -83.00   0.50   16.00    -- -104.00 109.00 166.76   50
 45  \w   -108.00 -83.00   0.50   16.00    -- -104.00 111.00  70.71   50
 46  \w     83.00 108.00   0.50   16.00    --  106.93-111.00 -54.49   50
 47  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 48  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 49  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 50  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 51  \w    -44.00 -19.00   0.50   15.00    --  -48.26  60.00-178.00   50
 52  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 53  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 54  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 55  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 56  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 57  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 58  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 59  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 60  \w    -44.00 -19.00   0.50   15.00    --  -48.26  60.00-178.00   50
 61  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 62  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 63  \w     53.00  78.00   0.50   15.00    --   48.26  60.00-178.00   50
 64  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 65  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 66  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 67  \w    -44.00 -19.00   0.50   15.00    --  -48.26  60.00-178.00   50
 68  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 69  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 70  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 71  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 72  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 73  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 74  \w   -156.00-131.00   0.50   16.00    -- -104.00 -60.00  41.00   50
 75  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 76  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 77  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 78  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 79  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 80  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 81  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
 82  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 83  \w    -68.00 -43.00   0.50   16.00    -- -104.00  60.00-178.00   50
 84  \w     53.00  78.00   0.50   15.00    --   48.26  60.00-178.00   50
 85  \w     35.00  60.00   0.50   16.00    --  106.93 -60.00  41.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0975730000
_diffrn_orient_matrix_UB_12      -0.0140767000
_diffrn_orient_matrix_UB_13      -0.0204745000
_diffrn_orient_matrix_UB_21      -0.0596407000
_diffrn_orient_matrix_UB_22      0.0766226000
_diffrn_orient_matrix_UB_23      0.0542049000
_diffrn_orient_matrix_UB_31      0.0140121000
_diffrn_orient_matrix_UB_32      0.0714237000
_diffrn_orient_matrix_UB_33      -0.0580472000
_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  0.0347
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            78964
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.456
_diffrn_reflns_theta_min         2.352
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.452
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64039
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.55a (Rigaku Oxford Diffraction, 2022)
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    1.042
_exptl_crystal_description       block
_exptl_crystal_F_000             1288
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.553
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     986
_refine_ls_number_reflns         15613
_refine_ls_number_restraints     503
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.0740
_refine_ls_R_factor_gt           0.0656
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1291P)^2^+0.7508P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1843
_refine_ls_wR_factor_ref         0.1923
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13013
_reflns_number_total             15613
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06470k2.cif
_cod_data_source_block           exp_1058_auto
_cod_depositor_comments          'Adding full bibliography for 1570793.cif.'
_cod_database_code               1570793
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H N B'
_chemical_oxdiff_usercomment     'C H N B'
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.935
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C61-C59 = C61A-C59 = C90-C87 = C90A-C87
 1.5 with sigma of 0.01
 H33B-C33
 1.54 with sigma of 0.01
 C91A-C90A = C92A-C90A = C92-C90 = C93A-C90A = C93-C90 = C91-C90
 1.54 with sigma of 0.01
 C92-C91 \\sim C93-C92 \\sim C93-C91
 with sigma of 0.02
 C50-C49 \\sim C51-C49 \\sim C51-C50
 with sigma of 0.02
 C63-C62 \\sim C64-C63 \\sim C64-C62
 with sigma of 0.02
 C57-C56 \\sim C57-C55 \\sim C56-C55
 with sigma of 0.02
 C93A-C92A \\sim C92A-C91A \\sim C93A-C91A
 with sigma of 0.02
 C63A-C62A \\sim C64A-C63A \\sim C64A-C62A
 with sigma of 0.02
 C51A-C50A \\sim C51A-C49A \\sim C50A-C49A
 with sigma of 0.02
 C56A-C55A \\sim C57A-C56A \\sim C57A-C55A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C61 \\sim C62 \\sim C63 \\sim C64 \\sim C61A \\sim C62A \\sim C63A \\sim C64A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C90 \\sim C91 \\sim C92 \\sim C93 \\sim C90A \\sim C91A \\sim C92A \\sim C93A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C55 \\sim C57 \\sim C56 \\sim C55A \\sim C57A \\sim C56A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C49 \\sim C50 \\sim C51 \\sim C49A \\sim C50A \\sim C51A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C48, C49, C50, C51, C49A, C50A, C51A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C87, C90, C91, C92, C93, C90A, C91A, C92A, C93A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C61, C62, C63, C64, C61A, C62A, C63A, C64A, C59
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C53, C55, C57, C56, C55A, C57A, C56A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(C61A)=Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C63A)=Sof(H63D)=
 Sof(H63E)=Sof(H63F)=Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=1-FVAR(1)
 Sof(C61)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=Sof(H63B)=
 Sof(H63C)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(1)
 Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=Sof(C57A)=Sof(H57D)=Sof(H57E)=
 Sof(H57F)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(2)
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(2)
 Sof(C49A)=Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C50A)=Sof(H50D)=Sof(H50E)=
 Sof(H50F)=Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=1-FVAR(3)
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(3)
 Sof(C90A)=Sof(C91A)=Sof(H91D)=Sof(H91E)=Sof(H91F)=Sof(C92A)=Sof(H92D)=
 Sof(H92E)=Sof(H92F)=Sof(C93A)=Sof(H93D)=Sof(H93E)=Sof(H93F)=1-FVAR(4)
 Sof(C90)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=Sof(C92)=Sof(H92A)=Sof(H92B)=
 Sof(H92C)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=FVAR(4)
6.a Aromatic/amide H refined with riding coordinates:
 C72(H72), C21(H21), C89(H89), C76(H76), C26(H26), C37(H37), C20(H20),
 C18(H18), C60(H60), C71(H71), C58(H58), C23(H23), C44(H44), C74(H74), C24(H24),
  C40(H40), C38(H38), C69(H69), C47(H47), C88(H88), C86(H86), C45(H45)
6.b Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C81(H81A,H81B,
 H81C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C29(H29A,H29B,H29C), C34(H34A,
 H34B,H34C), C30(H30A,H30B,H30C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C),
 C85(H85A,H85B,H85C), C62(H62A,H62B,H62C), C91(H91A,H91B,H91C), C63(H63A,H63B,
 H63C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C), C64(H64A,H64B,H64C), C51(H51A,H51B,H51C), C55(H55A,H55B,H55C),
 C57(H57A,H57B,H57C), C56(H56A,H56B,H56C), C62A(H62D,H62E,H62F), C63A(H63D,H63E,
 H63F), C64A(H64D,H64E,H64F), C55A(H55D,H55E,H55F), C57A(H57D,H57E,H57F),
 C56A(H56D,H56E,H56F), C49A(H49D,H49E,H49F), C50A(H50D,H50E,H50F), C51A(H51D,
 H51E,H51F), C91A(H91D,H91E,H91F), C92A(H92D,H92E,H92F), C93A(H93D,H93E,H93F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              93751
_shelx_fab_checksum              87019
_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 1.858
_oxdiff_exptl_absorpt_empirical_full_min 0.617