Pentacyclic fused diborepinium ions with carbene- and carbone-mediated deep-blue to red emission.
Hollister, Kimberly K.; Molino, Andrew; Le, VuongVy V; Jones, Nula; Smith, Wyatt J.; Müller, Peter; Dickie, Diane A.; Wilson, David J. D.; Gilliard, Jr, Robert J; Chemical science 15 (2024) 14358–14370; doi:10.1039/d4sc03835e

data_1572281
_publ_section_title
;
 Pentacyclic fused diborepinium ions with carbene- and carbone-mediated
 deep-blue to red emission.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              14358
_journal_page_last               14370
_journal_paper_doi               10.1039/d4sc03835e
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C33 H42 B Cl N, 2(C4 H8 O)'
_chemical_formula_sum            'C41 H58 B Cl N O2'
_chemical_formula_weight         643.14
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-03-28 deposited with the CCDC.	2024-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.779(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.7297(12)
_cell_length_b                   18.7599(8)
_cell_length_c                   15.6595(7)
_cell_measurement_reflns_used    9728
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      33.696
_cell_measurement_theta_min      2.538
_cell_volume                     7198.0(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing.cell_refinement       'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service V6.2.14'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing.data_reduction        'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing.structure_refinement  'SHELXL--2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_computing.structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.3910
_diffrn_detector_type            'Photon III'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'Kappa four--circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'one pinhole collimator 0.8 mm'
_diffrn_radiation_monochromator  'HELIOS double bounce multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0582
_diffrn_reflns_av_unetI/netI     0.0449
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            83023
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns.reduction_process narrow-frame
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.788
_diffrn_reflns_theta_min         1.972
_diffrn_source                   'micro-focus sealed tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\mS 3.0'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.142
_exptl_absorpt_correction_T_max  0.7467
_exptl_absorpt_correction_T_min  0.6126
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1317 before and 0.0643 after correction.
The Ratio of minimum to maximum transmission is 0.8204.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.187
_exptl_crystal_description       block
_exptl_crystal_F_000             2792
_exptl_crystal_size_max          0.453
_exptl_crystal_size_mid          0.426
_exptl_crystal_size_min          0.202
_refine_diff_density_max         0.856
_refine_diff_density_min         -1.174
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     444
_refine_ls_number_reflns         14377
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0825
_refine_ls_R_factor_gt           0.0611
_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^)+(0.0964P)^2^+8.5487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1666
_refine_ls_wR_factor_ref         0.1917
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11072
_reflns_number_total             14377
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03835e2.cif
_cod_data_source_block           2Cl
_cod_depositor_comments
'Adding full bibliography for 1572276--1572287.cif.'
_cod_database_code               1572281
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.938
_computing.bruker_data_scaling
'SADABS--2016/2 -- Bruker AXS area detector scaling and absorption correction'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39C)=Sof(H39D)=1-FVAR(1)
 Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=FVAR(1)
 Sof(H35C)=Sof(H35D)=Sof(H37C)=Sof(H37D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=1-FVAR(2)
 Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H37A)=Sof(H37B)=FVAR(2)
3.a Ternary CH refined with riding coordinates:
 C24(H24), C31(H31)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C16(H16A,H16B), C18(H18A,H18B), C34(H34A,H34B), C35(H35A,
 H35B), C35(H35C,H35D), C36(H36A,H36B), C37(H37A,H37B), C37(H37C,H37D),
 C38(H38A,H38B), C38(H38C,H38D), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B),
  C39A(H39C,H39D), C36A(H36C,H36D)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C27(H27), C28(H28),
 C29(H29)
3.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C)
;
_shelx_res_checksum              29649
_shelx_hkl_checksum              36813
_olex2_submission_special_instructions 'No special instructions were received'