Unexpected formation of α-formylated BOPHY in the reaction with copper salts
Prasannan, Dijo; Nemykin, Victor N.; New Journal of Chemistry 49 (2025) 19649–19655; doi:10.1039/D5NJ02748A

data_7064072
_publ_section_title
;
 Unexpected formation of \a-formylated BOPHY in the reaction with copper
 salts
;
_journal_issue                   45
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              19649
_journal_page_last               19655
_journal_paper_doi               10.1039/D5NJ02748A
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         '2(C21 H19 B Br F2 N5)'
_chemical_formula_sum            'C42 H38 B2 Br2 F4 N10'
_chemical_formula_weight         940.26
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-22
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-06-16 deposited with the CCDC.	2025-10-16 downloaded from the CCDC.
;
_cell_angle_alpha                98.094(6)
_cell_angle_beta                 93.490(6)
_cell_angle_gamma                118.563(5)
_cell_formula_units_Z            2
_cell_length_a                   13.1933(14)
_cell_length_b                   13.3860(13)
_cell_length_c                   13.7640(14)
_cell_measurement_reflns_used    2537
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      50.32
_cell_measurement_theta_min      5.19
_cell_volume                     2090.6(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.953
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0783
_diffrn_reflns_av_unetI/netI     0.1032
_diffrn_reflns_Laue_measured_fraction_full 0.953
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            9642
_diffrn_reflns_point_group_measured_fraction_full 0.953
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        50.538
_diffrn_reflns_theta_max         50.538
_diffrn_reflns_theta_min         5.190
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.985
_exptl_absorpt_correction_T_max  0.7500
_exptl_absorpt_correction_T_min  0.4755
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1291 before and 0.0694 after correction.
The Ratio of minimum to maximum transmission is 0.6340.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.034
_exptl_crystal_size_min          0.017
_refine_diff_density_max         1.086
_refine_diff_density_min         -0.726
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     437
_refine_ls_number_reflns         4192
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.1330
_refine_ls_R_factor_gt           0.0957
_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^)+(0.0851P)^2^+15.7737P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2081
_refine_ls_wR_factor_ref         0.2286
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3007
_reflns_number_total             4192
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj02748a2.cif
_cod_data_source_block           cu_dijo_bophy_alkyne_0m_a
_cod_depositor_comments
'Adding full bibliography for 7064069--7064073.cif.'
_cod_database_code               7064072
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.951
_shelx_estimated_absorpt_t_min   0.581
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C23) = Uanis(C1) = Uanis(C2) = Uanis(C4)
Uanis(C18) = Uanis(C7) = Uanis(C8) = Uanis(C9)
Uanis(C26) = Uanis(C12) = Uanis(C8) = Uanis(C15)
Uanis(C34) = Uanis(C30) = Uanis(C37) = Uanis(C38) = Uanis(C29)
Uanis(C17) = Uanis(C36)
Uanis(B2) = Uanis(B1)
Uanis(F5) = Uanis(F4) = Uanis(F2) = Uanis(F1)
Uanis(N7) = Uanis(N4) = Uanis(N3)
Uanis(N6) = Uanis(N4) = Uanis(N3) = Uanis(N2) = Uanis(N7) = Uanis(N8)
Uanis(Br2) = Uanis(Br4)
3. Others
 Sof(H38)=Sof(Br4)=1-FVAR(1)
 Sof(H34)=Sof(Br2)=FVAR(1)
 Sof(H11)=Sof(Br3)=1-FVAR(2)
 Sof(H17)=Sof(Br1)=FVAR(2)
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C14(H14), C17(H17), C31(H31),
 C34(H34), C38(H38), N5(H5A), N10(H10)
4.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C)
;
_shelx_res_checksum              11533
_olex2_submission_special_instructions 'No special instructions were received'