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_1567980
_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 H108 P2'
_chemical_formula_sum            'C54 H108 P2'
_chemical_formula_weight         819.34
_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     direct
_audit_creation_date             2016-08-26
_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                90
_cell_angle_beta                 96.694(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   45.099(2)
_cell_length_b                   12.6445(7)
_cell_length_c                   9.3990(5)
_cell_measurement_reflns_used    9968
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      40.397
_cell_measurement_theta_min      3.632
_cell_volume                     5323.3(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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 0.994
_diffrn_measured_fraction_theta_max 0.994
_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  0.0658
_diffrn_reflns_av_unetI/netI     0.0281
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       53
_diffrn_reflns_limit_h_min       -52
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            46796
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        65.273
_diffrn_reflns_theta_max         65.273
_diffrn_reflns_theta_min         3.632
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.953
_exptl_absorpt_correction_T_max  0.7479
_exptl_absorpt_correction_T_min  0.6395
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014/3) was used for absorption correction.
wR2(int) was 0.1170 before and 0.0600 after correction.
The Ratio of minimum to maximum transmission is 0.8551.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.022
_exptl_crystal_description       plate
_exptl_crystal_F_000             1848
_exptl_crystal_size_max          0.244
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.387
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         4543
_refine_ls_number_restraints     1693
_refine_ls_restrained_S_all      1.430
_refine_ls_R_factor_all          0.0741
_refine_ls_R_factor_gt           0.0604
_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^)+(0.0661P)^2^+6.3824P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1447
_refine_ls_wR_factor_ref         0.1557
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3684
_reflns_number_total             4543
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04724a3.cif
_cod_data_source_block           hjsk18c
_cod_database_code               1567980
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.801
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C10-C11 \\sim C11-C12 \\sim C12-C13 \\sim C13-C14 \\sim C14-C15 \\sim C15-C16
\\sim C16-C17 \\sim C17-C18
 \\sim C18-C19 \\sim C19-C20 \\sim C20-C21 \\sim C21-C22 \\sim C22-C23 \\sim
C23-C24 \\sim C24-C25 \\sim C25-
 C26 \\sim C26-C27 \\sim C10-C11A \\sim C11A-C12A \\sim C12A-C13A \\sim
C13A-C14A \\sim C14A-C15A ~
 C15A-C16A \\sim C16A-C17A \\sim C17A-C18A \\sim C18A-C19A \\sim C19A-C20A
\\sim C20A-C21A \\sim C21A-
 C22A \\sim C22A-C23A \\sim C23A-C24A \\sim C24A-C25A \\sim C25A-C26A \\sim
C26A-C27
 with sigma of 0.01
 C10-C12 \\sim C11-C13 \\sim C12-C14 \\sim C13-C15 \\sim C14-C16 \\sim C15-C17
\\sim C16-C18 \\sim C17-C19
 \\sim C18-C20 \\sim C19-C21 \\sim C20-C22 \\sim C21-C23 \\sim C22-C24 \\sim
C23-C25 \\sim C24-C26 \\sim C25-
 C27 \\sim C10-C12A \\sim C11A-C13A \\sim C12A-C14A \\sim C13A-C15A \\sim
C14A-C16A \\sim C15A-C17A ~
 C16A-C18A \\sim C17A-C19A \\sim C18A-C20A \\sim C19A-C21A \\sim C20A-C22A
\\sim C21A-C23A \\sim C22A-
 C24A \\sim C23A-C25A \\sim C24A-C26A \\sim C25A-C27
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim
C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim
C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim C16A \\sim C17A \\sim
C18A \\sim C19A \\sim C20A \\sim C21A \\sim C22A \\sim C23A \\sim C24A \\sim
C25A \\sim C26A: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04
Uanis(C11) = Uanis(C11A)
4. Rigid body (RIGU) restrains
 C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25,
 C26, C11A, C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A, C21A, C22A,
 C23A, C24A, C25A, C26A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
5. Others
 Sof(H10C)=Sof(H10D)=Sof(H27C)=Sof(H27D)=Sof(C11A)=Sof(H11C)=Sof(H11D)=
 Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C14A)=
 Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=Sof(C16A)=Sof(H16C)=
 Sof(H16D)=Sof(C17A)=Sof(H17C)=Sof(H17D)=Sof(C18A)=Sof(H18C)=Sof(H18D)=
 Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20C)=Sof(H20D)=Sof(C21A)=
 Sof(H21C)=Sof(H21D)=Sof(C22A)=Sof(H22C)=Sof(H22D)=Sof(C23A)=Sof(H23C)=
 Sof(H23D)=Sof(C24A)=Sof(H24C)=Sof(H24D)=Sof(C25A)=Sof(H25C)=Sof(H25D)=
 Sof(C26A)=Sof(H26C)=Sof(H26D)=1-FVAR(1)
 Sof(H10A)=Sof(H10B)=Sof(H27A)=Sof(H27B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=
 Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=
 Sof(H17B)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=
 Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(C25)=Sof(H25A)=
 Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C10(H10C,H10D),
 C27(H27A,H27B), C27(H27C,H27D), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B),
  C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,
 H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B),
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C11A(H11C,
 H11D), C12A(H12C,H12D), C13A(H13C,H13D), C14A(H14C,H14D), C15A(H15C,H15D),
 C16A(H16C,H16D), C17A(H17C,H17D), C18A(H18C,H18D), C19A(H19C,H19D), C20A(H20C,
 H20D), C21A(H21C,H21D), C22A(H22C,H22D), C23A(H23C,H23D), C24A(H24C,H24D),
 C25A(H25C,H25D), C26A(H26C,H26D)
;
_shelx_res_checksum              73630
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'