Di-π-methane rearrangement in 1-phosphabarrelenes: formation and reactivity of an unprecedented 2-phosphasemibullvalene.
Steffen, Leo; Szych, Lilian S.; Franzke, Yannick J.; Kopp, Richard O.; Ernst, Moritz J.; Weber, Manuela; Müller, Christian; Chemical communications (Cambridge, England) 61 (2025) 14907–14910; doi:10.1039/d5cc04015a

data_7134904
_publ_section_title
;
 Di-&#x3c0;-methane rearrangement in 1-phosphabarrelenes: formation and
 reactivity of an unprecedented 2-phosphasemibullvalene.
;
_journal_issue                   77
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              14907
_journal_page_last               14910
_journal_paper_doi               10.1039/d5cc04015a
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C17 H13 P'
_chemical_formula_sum            'C17 H13 P'
_chemical_formula_weight         248.24
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-09
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-09 deposited with the CCDC.	2025-08-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.0423(10)
_cell_length_b                   7.6100(3)
_cell_length_c                   7.1438(3)
_cell_measurement_reflns_used    3780
_cell_measurement_temperature    140.00
_cell_measurement_theta_max      68.13
_cell_measurement_theta_min      3.68
_cell_volume                     1307.04(9)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      140.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0636
_diffrn_reflns_av_unetI/netI     0.0566
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            5233
_diffrn_reflns_point_group_measured_fraction_full 0.953
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.124
_diffrn_reflns_theta_min         3.677
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.658
_exptl_absorpt_correction_T_max  0.7632
_exptl_absorpt_correction_T_min  0.3911
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1660 before and 0.1126 after correction.
The Ratio of minimum to maximum transmission is 0.5124.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_description       needle
_exptl_crystal_F_000             520
_exptl_crystal_size_max          0.63
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.788
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.326
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.17(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     86
_refine_ls_number_reflns         1175
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0777
_refine_ls_R_factor_gt           0.0719
_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^)+(0.1002P)^2^+2.6523P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1700
_refine_ls_wR_factor_ref         0.1778
_reflns_Friedel_coverage         0.749
_reflns_Friedel_fraction_full    0.899
_reflns_Friedel_fraction_max     0.900
_reflns_number_gt                1087
_reflns_number_total             1175
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc04015a2.cif
_cod_data_source_block           leo36-all_a
_cod_depositor_comments
'Adding full bibliography for 7134904--7134908.cif.'
_cod_database_code               7134904
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.422
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.83(8)
 0.17(8)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9)
;
_shelx_res_checksum              28887
_shelx_hkl_checksum              52213
_olex2_submission_special_instructions 'No special instructions were received'