Optically-pure triptycene-based metallomacrocycles and homochiral self-sorting assisted by ladder formation
Oki, Kosuke; Zheng, Wei; Yashima, Eiji; Ikai, Tomoyuki; Chemical Communications  (2023) –; doi:10.1039/D3CC02259E

data_7131789
_publ_section_title
;
 Optically-pure triptycene-based metallomacrocycles and homochiral
 self-sorting assisted by ladder formation
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC02259E
_journal_year                    2023
_chemical_formula_moiety         'C128 H140 N4 O4 P4 Pt2, 4(C F3 O3 S)'
_chemical_formula_sum            'C132 H140 F12 N4 O16 P4 Pt2 S4'
_chemical_formula_weight         2908.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yc'
_space_group_name_H-M_alt        'P 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-04-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-04-22 deposited with the CCDC.	2023-06-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.581(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.7093(5)
_cell_length_b                   16.7013(6)
_cell_length_c                   23.8942(6)
_cell_measurement_reflns_used    9400
_cell_measurement_temperature    93
_cell_measurement_theta_max      24.9710
_cell_measurement_theta_min      1.6900
_cell_volume                     7064.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      93.0
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

 # Type Start End Width t~exp~ \w \q \k \f Frames
 1 \w -14.00 78.00 0.50 120.00 -- 5.81 77.00 60.00 184
 2 \w -38.00 10.00 0.50 120.00 -- 5.81 -57.00 90.00 96
 3 \w -6.00 32.00 0.50 120.00 -- 5.81 -99.00-150.00 76
 4 \w -64.00 10.00 0.50 120.00 -- -4.17 -57.00-180.00 148
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0102147000
_diffrn_orient_matrix_UB_12      0.0199995000
_diffrn_orient_matrix_UB_13      0.0252886000
_diffrn_orient_matrix_UB_21      0.0098582000
_diffrn_orient_matrix_UB_22      -0.0372324000
_diffrn_orient_matrix_UB_23      0.0124811000
_diffrn_orient_matrix_UB_31      0.0374612000
_diffrn_orient_matrix_UB_32      0.0042993000
_diffrn_orient_matrix_UB_33      -0.0092951000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0824
_diffrn_reflns_av_unetI/netI     0.0718
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            52497
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.499
_diffrn_reflns_theta_min         1.676
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Mova (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.157
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58712
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_description       needle
_exptl_crystal_F_000             2952
_exptl_crystal_size_max          0.159
_exptl_crystal_size_mid          0.051
_exptl_crystal_size_min          0.036
_refine_diff_density_max         1.909
_refine_diff_density_min         -1.018
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1053
_refine_ls_number_reflns         13158
_refine_ls_number_restraints     1528
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.1520
_refine_ls_R_factor_gt           0.0891
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1726P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2502
_refine_ls_wR_factor_ref         0.2807
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7129
_reflns_number_total             13158
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc02259e2.cif
_cod_data_source_block           metallacycle
_cod_database_code               7131789
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C264 H280 F24 N8 O32 P8 Pt4 S8'
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.725
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-C37 = C37-C38 = C38-C39 = C39-C40 = C40-C41 = C41-C36 = C45-C46 = C46-C47
 = C47-C48 = C48-C49 = C49-C50 = C50-C45 = C45-C100 = C100-C101 = C101-C48 =
 C48-C102 = C102-C103 = C103-C45 = C36A-C37A = C37A-C38A = C38A-C39A = C39A-
 C40A = C40A-C41A = C41A-C36A
 1.39 with sigma of 0.02
 C42-C43 = C43-C44 = C51-C52 = C52-C53 = C51A-C52A = C52A-C53A = C42A-C43A =
 C43A-C44A
 1.54 with sigma of 0.02
 O1-C42 = O1A-C42A = O2-C51 = O2-C51A
 1.43 with sigma of 0.02
 C42-C44 = C42A-C44A = C51-C53 = C51A-C53A
 2.49 with sigma of 0.02
 O1-C43 \\sim O1A-C43A
 with sigma of 0.02
 C54-C55 \\sim C56-C57 \\sim C56-C57 \\sim C58-C59 \\sim C60-C61 \\sim C62-C63
\\sim C62-C63 \\sim C64-C65
 \\sim C62-C63 \\sim C64-C65A
 with sigma of 0.02
 C7-O10 \\sim C7-O11 \\sim C7-O11 \\sim C7-O12 \\sim C7A-O10A \\sim C7A-O11A
\\sim C7A-O11A \\sim C7A-O12A
 with sigma of 0.02
 C7-F4 \\sim C7-F5 \\sim C7-F5 \\sim C7-F6 \\sim C7A-F4A \\sim C7A-F5A \\sim
C7A-F5A \\sim C7A-F6A
 with sigma of 0.02
 F4-F5 \\sim F5-F6 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim
F5A-F6A \\sim F6A-F4A
 with sigma of 0.02
 S2-O10 \\sim S2-O11 \\sim S2-O11 \\sim S2-O12 \\sim S2A-O10A \\sim S2A-O11A
\\sim S2A-O11A \\sim S2A-O12A
 with sigma of 0.02
 O10-O11 \\sim O11-O12 \\sim O11-O12 \\sim O12-O10 \\sim O10A-O11A \\sim
O11A-O12A \\sim O11A-O12A ~
 O12A-O10A
 with sigma of 0.02
 C7-S2 \\sim C7A-S2A
 with sigma of 0.02
 C36-C38 \\sim C37-C39 \\sim C37-C39 \\sim C38-C40 \\sim C38-C40 \\sim C39-C41
\\sim C39-C41 \\sim C40-C36
 \\sim C40-C36 \\sim C41-C37 \\sim C36A-C38A \\sim C37A-C39A \\sim C37A-C39A
\\sim C38A-C40A \\sim C38A-
 C40A \\sim C39A-C41A \\sim C39A-C41A \\sim C40A-C36A \\sim C40A-C36A \\sim
C41A-C37A
 with sigma of 0.02
 N1-Pt1 \\sim N1-Pt1A \\sim N1-Pt1 \\sim N1-Pt1B
 with sigma of 0.02
3. Rigid bond restraints
 C45, C48, C46, C47, C49, C50, C100, C101, C102, C103
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C51, C52, C53, C51A, C52A, C53A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C36, C37, C38, C39, C40, C41, C42, C43, C44, O1, C36A, C37A, C38A, C39A, C40A,
  C41A, C42A, C43A, C44A, O1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C64, C65, C65A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C7, F4, F5, F6, S2, O10, O11, O12, C7A, F4A, F5A, F6A, S2A, O10A, O11A, O12A
 with sigma for 1-2 distances of 0.04 and sigma for 1-3 distances of 0.04
 Pt1, Pt1A, Pt1B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1, C2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C45 \\sim C48 \\sim C46 \\sim C47 \\sim C49 \\sim C50 \\sim C100 \\sim C101
\\sim C102 \\sim C103: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
C51 \\sim C52 \\sim C53 \\sim C51A \\sim C52A \\sim C53A: within 2A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 2A
C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim
C44 \\sim O1 \\sim C36A \\sim C37A \\sim C38A \\sim C39A \\sim C40A \\sim C41A
\\sim C42A \\sim C43A \\sim C44A \\sim O1A: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C64 \\sim C65 \\sim C65A: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
C7 \\sim F4 \\sim F5 \\sim F6 \\sim S2 \\sim O10 \\sim O11 \\sim O12 \\sim C7A
\\sim F4A \\sim F5A \\sim F6A \\sim S2A \\sim O10A \\sim O11A \\sim O12A:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
Pt1 \\sim Pt1A \\sim Pt1B: within 2A with sigma of 0.03 and sigma for terminal
atoms of 0.06 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6: within 2A with sigma of 0.03
and sigma for terminal atoms of 0.06 within 2A
Uanis(C45) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C100) \\sim Ueq,
Uanis(C101) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C103) \\sim Ueq: with sigma
of 0.03 and sigma for terminal atoms of 0.06
Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C51A)
\\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C53A) \\sim Ueq: with sigma of 0.03 and
sigma for terminal atoms of 0.06
Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C36A)
\\sim Ueq, Uanis(C37A) \\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(C39A) \\sim Ueq,
Uanis(C40A) \\sim Ueq, Uanis(C41A) \\sim Ueq, Uanis(C42A) \\sim Ueq,
Uanis(C43A) \\sim Ueq, Uanis(C44A) \\sim Ueq, Uanis(O1A) \\sim Ueq: with sigma
of 0.03 and sigma for terminal atoms of 0.06
Uanis(C64) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C65A) \\sim Ueq: with sigma
of 0.03 and sigma for terminal atoms of 0.06
Uanis(C7) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq, Uanis(F6) \\sim
Ueq, Uanis(S2) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(O11) \\sim Ueq,
Uanis(O12) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(F5A)
\\sim Ueq, Uanis(F6A) \\sim Ueq, Uanis(S2A) \\sim Ueq, Uanis(O10A) \\sim Ueq,
Uanis(O11A) \\sim Ueq, Uanis(O12A) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(Pt1) \\sim Ueq, Uanis(Pt1A) \\sim Ueq, Uanis(Pt1B) \\sim Ueq: with sigma
of 0.04 and sigma for terminal atoms of 0.08
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.03 and sigma for
terminal atoms of 0.06
5. Same fragment restrains
{C66, F1, F2, F3, S004, O3, O4, O5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C7, F4, F5, F6, S2, O10, O11, O12}
{C66, F1, F2, F3, S004, O3, O4, O5} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C7A, F4A, F5A, F6A, S2A, O10A, O11A, O12A}
6. Others
 1*[Sof(Pt1)]+1*[Sof(Pt1A)]+1*[Sof(Pt1B)]=1 with esd of 0.0001
 Sof(C100)=Sof(H100)=Sof(C101)=Sof(H101)=Sof(C102)=Sof(H102)=Sof(C103)=
 Sof(H103)=1-FVAR(1)
 Sof(C46)=Sof(H46)=Sof(C47)=Sof(H47)=Sof(C49)=Sof(H49)=Sof(C50)=Sof(H50)=FVAR(1)
 Sof(C51A)=Sof(H51C)=Sof(H51D)=Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=
 Sof(H53D)=Sof(H53E)=Sof(H53F)=1-FVAR(2)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(H53C)=FVAR(2)
 Sof(C36A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(C40A)=
 Sof(H40A)=Sof(C41A)=Sof(H41A)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=
 Sof(H43C)=Sof(H43D)=Sof(C44A)=Sof(H44D)=Sof(H44E)=Sof(H44F)=Sof(O1A)=Sof(H64C)=
 Sof(H64D)=Sof(C65A)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C7A)=Sof(F4A)=Sof(F5A)=
 Sof(F6A)=Sof(S2A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=1-FVAR(4)
 Sof(C36)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(C40)=Sof(H40)=
 Sof(C41)=Sof(H41)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(O1)=Sof(H64A)=Sof(H64B)=Sof(C65)=
 Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C7)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(S2)=Sof(O10)=
 Sof(O11)=Sof(O12)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 C21(H21), C35(H35)
7.b Secondary CH2 refined with riding coordinates:
 C51(H51A,H51B), C52(H52A,H52B), C51A(H51C,H51D), C52A(H52C,H52D), C42(H42A,
 H42B), C43(H43A,H43B), C42A(H42C,H42D), C43A(H43C,H43D), C54(H54A,H54B),
 C56(H56A,H56B), C58(H58A,H58B), C60(H60A,H60B), C62(H62A,H62B), C64(H64A,H64B),
  C64(H64C,H64D)
7.c Aromatic/amide H refined with riding coordinates:
 C46(H46), C47(H47), C49(H49), C50(H50), C100(H100), C101(H101), C102(H102),
 C103(H103), C37(H37), C38(H38), C40(H40), C41(H41), C37A(H37A), C38A(H38A),
 C40A(H40A), C41A(H41A), C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C12(H12),
 C13(H13), C14(H14), C16(H16), C19(H19), C23(H23), C26(H26), C27(H27), C28(H28),
  C30(H30), C33(H33)
7.d Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C53A(H53D,H53E,H53F), C44(H44A,H44B,H44C), C44A(H44D,
 H44E,H44F), C55(H55A,H55B,H55C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C),
 C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C), C65A(H65D,H65E,
 H65F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6460
_shelx_hkl_checksum              80965
_shelx_fab_checksum              72189
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.649
_oxdiff_exptl_absorpt_empirical_full_min 0.704