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_1572284
_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         'C32 H12 B F24.014, C33 H42 B N'
_chemical_formula_sum            'C65 H54 B2 F24.01 N'
_chemical_formula_weight         1326.99
_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             2021-12-06
_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                85.418(2)
_cell_angle_beta                 79.658(2)
_cell_angle_gamma                73.127(2)
_cell_formula_units_Z            2
_cell_length_a                   12.5802(15)
_cell_length_b                   13.1420(16)
_cell_length_c                   19.744(2)
_cell_measurement_reflns_used    9807
_cell_measurement_temperature    100.03
_cell_measurement_theta_max      33.234
_cell_measurement_theta_min      2.407
_cell_volume                     3071.6(6)
_computing_cell_refinement       'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_computing.cell_refinement       'SAINT V8.40B (Bruker Nano, Inc., 2019)'
_computing_data_collection       'Bruker Instrument Service v2017.5.0.0'
_computing_data_reduction        'SAINT V8.40A (Bruker Nano, Inc., 2019)'
_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, 2018)'
_computing.structure_refinement  'SHELXL--2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_computing.structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.03
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    'one pinhole collimator 0.8 mm'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0452
_diffrn_reflns_av_unetI/netI     0.0399
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            119222
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns.reduction_process narrow-frame
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         33.751
_diffrn_reflns_theta_min         1.620
_diffrn_source                   'fine-focus sealed tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Cu
_diffrn_source_type              'Incoatec I\mS 3.0'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.134
_exptl_absorpt_correction_T_max  0.7467
_exptl_absorpt_correction_T_min  0.6992
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0487 before and 0.0448 after correction.
The Ratio of minimum to maximum transmission is 0.9364.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.435
_exptl_crystal_description       plate
_exptl_crystal_F_000             1354
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.548
_refine_diff_density_min         -0.459
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     938
_refine_ls_number_reflns         24545
_refine_ls_number_restraints     187
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0858
_refine_ls_R_factor_gt           0.0516
_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^)+(0.0656P)^2^+1.1031P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1239
_refine_ls_wR_factor_ref         0.1440
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16860
_reflns_number_total             24545
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03835e2.cif
_cod_data_source_block           5
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1572276--1572287.cif.
;
_cod_database_code               1572284
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.961
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
F23A \\sim F23 \\sim F23B \\sim F24 \\sim F24A \\sim F24B \\sim F22A \\sim F22B
\\sim F22: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
F7A \\sim F7 \\sim F7B \\sim F8B \\sim F8 \\sim F8A \\sim F9B \\sim F9 \\sim
F9A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(F7) = Uanis(F7A) = Uanis(F7B)
3. Others
 1*[Sof(F1)+Sof(F2)+Sof(F3)+Sof(F4)+Sof(F5)+Sof(F6)+Sof(F10)+Sof(F11)+Sof(F12)+
 Sof(F13)+Sof(F14)+Sof(F15)+Sof(F16)+Sof(F17)+Sof(F18)+Sof(F19)+Sof(F20)+
 Sof(F21)+Sof(F22)+Sof(F23)+Sof(F24)+Sof(C34)+Sof(C35)+Sof(H35)+Sof(C36)+
 Sof(C37)+Sof(C38)+Sof(H38)+Sof(C39)+Sof(C40)+Sof(C41)+Sof(H41)+Sof(C42)+
 Sof(C43)+Sof(H43)+Sof(C44)+Sof(C45)+Sof(C46)+Sof(H46)+Sof(C47)+Sof(C48)+
 Sof(C49)+Sof(H49)+Sof(C50)+Sof(C51)+Sof(H51)+Sof(C52)+Sof(C53)+Sof(C54)+
 Sof(H54)+Sof(C55)+Sof(C56)+Sof(C57)+Sof(H57)+Sof(C58)+Sof(C59)+Sof(H59)+
 Sof(C60)+Sof(C61)+Sof(C62)+Sof(H62)+Sof(C63)+Sof(C64)+Sof(C65)+Sof(H65)+
 Sof(B2)+Sof(N1)+Sof(C1)+Sof(C2)+Sof(H2)+Sof(C3)+Sof(C4)+Sof(H4)+Sof(C5)+
 Sof(H5)+Sof(C6)+Sof(C7)+Sof(H7)+Sof(C8)+Sof(H8)+Sof(C9)+Sof(H9)+Sof(C10)+
 Sof(H10)+Sof(C11)+Sof(C12)+Sof(C13)+Sof(C14)+Sof(H14A)+Sof(H14B)+Sof(C15)+
 Sof(H15A)+Sof(H15B)+Sof(H15C)+Sof(C16)+Sof(H16A)+Sof(H16B)+Sof(C17)+Sof(H17A)+
 Sof(H17B)+Sof(H17C)+Sof(C18)+Sof(H18A)+Sof(H18B)+Sof(C19)+Sof(C20)+Sof(H20A)+
 Sof(H20B)+Sof(H20C)+Sof(C21)+Sof(H21A)+Sof(H21B)+Sof(H21C)+Sof(C22)+Sof(C23)+
 Sof(C24)+Sof(H24)+Sof(C25)+Sof(H25A)+Sof(H25B)+Sof(H25C)+Sof(C26)+Sof(H26A)+
 Sof(H26B)+Sof(H26C)+Sof(C27)+Sof(H27)+Sof(C28)+Sof(H28)+Sof(C29)+Sof(H29)+
 Sof(C30)+Sof(C31)+Sof(H31)+Sof(C32)+Sof(H32A)+Sof(H32B)+Sof(H32C)+Sof(C33)+
 Sof(H33A)+Sof(H33B)+Sof(H33C)+Sof(B1)+Sof(Q1)+Sof(Q2)+Sof(Q3)+Sof(Q4)+Sof(Q5)+
 Sof(Q6)+Sof(Q7)]+1*[Sof(F24A)+Sof(F23A)+Sof(F22A)]+1*[Sof(F22B)+Sof(F23B)+
 Sof(F24B)]=1 with esd of 0.02
 1*[Sof(F7)+Sof(F8)+Sof(F9)]+1*[Sof(F8A)+Sof(F9A)+Sof(F7A)]+1*[Sof(F9B)+
 Sof(F8B)+Sof(F7B)]=1 with esd of 0.02
 Sof(F24A)=Sof(F23A)=Sof(F22A)=FVAR(1)
 Sof(F22B)=Sof(F23B)=Sof(F24B)=FVAR(2)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(F8A)=Sof(F9A)=Sof(F7A)=FVAR(4)
 Sof(F9B)=Sof(F8B)=Sof(F7B)=FVAR(5)
 Fixed Sof: F22(0.5) F23(0.5) F24(0.5)
4.a Ternary CH refined with riding coordinates:
 C24(H24), C31(H31)
4.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C16(H16A,H16B), C18(H18A,H18B)
4.c Aromatic/amide H refined with riding coordinates:
 C35(H35), C38(H38), C41(H41), C43(H43), C46(H46), C49(H49), C51(H51),
 C54(H54), C57(H57), C59(H59), C62(H62), C65(H65), C2(H2), C4(H4), C5(H5),
 C7(H7), C8(H8), C9(H9), C10(H10), C27(H27), C28(H28), C29(H29)
4.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              24
_shelx_hkl_checksum              37673
_olex2_submission_special_instructions 'No special instructions were received'