Syntheses, homeomorphic and configurational isomerizations, and structures of macrocyclic aliphatic dibridgehead diphosphines; molecules that turn themselves inside out
Zhu, Yun; Stollenz, Michael; Zarcone, Samuel R.; Kharel, Sugam; Joshi, Hemant; Bhuvanesh, Nattamai; Reibenspies, Joseph H.; Gladysz, John A.; Chemical Science  (2022) –; doi:10.1039/D2SC04724A

data_1567981
_publ_section_title
;
 Syntheses, homeomorphic and configurational isomerizations, and
 structures of macrocyclic aliphatic dibridgehead diphosphines; molecules
 that turn themselves inside out
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC04724A
_journal_year                    2022
_chemical_formula_moiety         'C54 H114 B2 P2'
_chemical_formula_sum            'C54 H114 B2 P2'
_chemical_formula_weight         847.01
_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     direct
_audit_creation_date             2017-03-31
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2022-07-14 deposited with the CCDC.	2022-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                81.639(3)
_cell_angle_beta                 85.640(3)
_cell_angle_gamma                87.030(3)
_cell_formula_units_Z            6
_cell_length_a                   9.0197(5)
_cell_length_b                   26.5241(15)
_cell_length_c                   35.839(2)
_cell_measurement_reflns_used    9744
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      63.074
_cell_measurement_theta_min      3.425
_cell_volume                     8451.2(8)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.981
_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  0.0970
_diffrn_reflns_av_unetI/netI     0.0848
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            58948
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        49.999
_diffrn_reflns_theta_max         49.999
_diffrn_reflns_theta_min         2.235
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.907
_exptl_absorpt_correction_T_max  0.7315
_exptl_absorpt_correction_T_min  0.6212
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1286 before and 0.0769 after correction.
The Ratio of minimum to maximum transmission is 0.8492.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.999
_exptl_crystal_description       block
_exptl_crystal_F_000             2868
_exptl_crystal_size_max          0.279
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.061
_refine_diff_density_max         0.384
_refine_diff_density_min         -0.508
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.254
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1573
_refine_ls_number_reflns         16992
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.254
_refine_ls_R_factor_all          0.1582
_refine_ls_R_factor_gt           0.1249
_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^)+52.3593P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2338
_refine_ls_wR_factor_ref         0.2478
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12463
_reflns_number_total             16992
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04724a3.cif
_cod_data_source_block           18cpbh3
_cod_database_code               1567981
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.786
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All B(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C20F \\sim C19F \\sim P1F: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
3. Rigid body (RIGU) restrains
 C19F, C20F, P1F
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4.a Secondary CH2 refined with riding coordinates:
 C19F(H19A,H19B), C2(H2A,H2B), C3F(H3FA,H3FB), C21(H21C,H21D), C35B(H35E,H35F),
  C22(H22C,H22D), C14(H14C,H14D), C41(H41C,H41D), C39(H39C,H39D), C7(H7A,H7B),
 C12(H12C,H12D), C50(H50C,H50D), C13(H13C,H13D), C48(H48C,H48D), C30B(H30E,
 H30F), C27B(H27E,H27F), C52(H52C,H52D), C40(H40C,H40D), C32(H32C,H32D), C5(H5A,
 H5B), C20F(H20A,H20B), C15(H15C,H15D), C35(H35C,H35D), C4(H4A,H4B), C30(H30C,
 H30D), C32B(H32E,H32F), C33(H33C,H33D), C6B(H6BA,H6BB), C26B(H26E,H26F),
 C47(H47C,H47D), C12F(H12A,H12B), C6F(H6FA,H6FB), C37(H37C,H37D), C24B(H24E,
 H24F), C34(H34C,H34D), C28B(H28E,H28F), C13F(H13A,H13B), C8(H8A,H8B), C6(H6A,
 H6B), C38(H38C,H38D), C42(H42C,H42D), C3(H3A,H3B), C29B(H29E,H29F), C14F(H14A,
 H14B), C1(H1A,H1B), C2F(H2FA,H2FB), C5F(H5FA,H5FB), C25B(H25E,H25F), C23(H23C,
 H23D), C25F(H25A,H25B), C26(H26C,H26D), C4F(H4FA,H4FB), C37B(H37E,H37F),
 C43(H43C,H43D), C46(H46C,H46D), C19(H19C,H19D), C17(H17C,H17D), C11(H11C,H11D),
  C50F(H50A,H50B), C49(H49C,H49D), C4B(H4BA,H4BB), C44(H44C,H44D), C1F(H1FA,
 H1FB), C1B(H1BA,H1BB), C9(H9A,H9B), C33B(H33E,H33F), C36(H36C,H36D), C18(H18C,
 H18D), C37F(H37A,H37B), C10(H10C,H10D), C24(H24C,H24D), C17F(H17A,H17B),
 C31(H31C,H31D), C45(H45C,H45D), C43F(H43A,H43B), C51(H51C,H51D), C16(H16C,
 H16D), C5B(H5BA,H5BB), C8F(H8FA,H8FB), C3B(H3BA,H3BB), C23B(H23E,H23F),
 C11F(H11A,H11B), C34B(H34E,H34F), C53(H53C,H53D), C48F(H48A,H48B), C45F(H45A,
 H45B), C2B(H2BA,H2BB), C19B(H19E,H19F), C22F(H22A,H22B), C10F(H10A,H10B),
 C52F(H52A,H52B), C9B(H9BA,H9BB), C28(H28C,H28D), C36F(H36A,H36B), C54F(H54A,
 H54B), C24F(H24A,H24B), C38B(H38E,H38F), C53F(H53A,H53B), C54B(H54E,H54F),
 C31B(H31E,H31F), C8B(H8BA,H8BB), C13B(H13E,H13F), C39F(H39A,H39B), C42B(H42E,
 H42F), C45B(H45E,H45F), C29(H29C,H29D), C16F(H16A,H16B), C40B(H40E,H40F),
 C51F(H51A,H51B), C7B(H7BA,H7BB), C21F(H21A,H21B), C42F(H42A,H42B), C17B(H17E,
 H17F), C41F(H41A,H41B), C25(H25C,H25D), C7F(H7FA,H7FB), C15F(H15A,H15B),
 C49F(H49A,H49B), C9F(H9FA,H9FB), C54(H54C,H54D), C10B(H10E,H10F), C32F(H32A,
 H32B), C44B(H44E,H44F), C11B(H11E,H11F), C38F(H38A,H38B), C18F(H18A,H18B),
 C20(H20C,H20D), C44F(H44A,H44B), C20B(H20E,H20F), C28F(H28A,H28B), C41B(H41E,
 H41F), C40F(H40A,H40B), C27(H27C,H27D), C46F(H46A,H46B), C43B(H43E,H43F),
 C22B(H22E,H22F), C33F(H33A,H33B), C12B(H12E,H12F), C47F(H47A,H47B), C53B(H53E,
 H53F), C23F(H23A,H23B), C15B(H15E,H15F), C27F(H27A,H27B), C48B(H48E,H48F),
 C35F(H35A,H35B), C31F(H31A,H31B), C34F(H34A,H34B), C39B(H39E,H39F), C30F(H30A,
 H30B), C50B(H50E,H50F), C14B(H14E,H14F), C49B(H49E,H49F), C46B(H46E,H46F),
 C52B(H52E,H52F), C16B(H16E,H16F), C21B(H21E,H21F), C47B(H47E,H47F), C51B(H51E,
 H51F), C36B(H36E,H36F), C18B(H18E,H18F), C29F(H29A,H29B), C26F(H26A,H26B)
4.b Idealised Me refined as rotating group:
 B2(H2C,H2D,H2E), B1F(H1FC,H1FD,H1FE), B1B(H1BC,H1BD,H1BE), B2F(H2FC,H2FD,
 H2FE), B1(H1C,H1D,H1E), B2B(H2BC,H2BD,H2BE)
;
_shelx_res_checksum              49880
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'