Host–guest binding of tetracationic cyclophanes to photodynamic agents inhibits posttreatment phototoxicity and maintains antitumour efficacy
Sun, Jian-Da; Liu, Yamin; Zhao, Zijian; Yu, Shang-Bo; Qi, Qiao-Yan; Zhou, Wei; Wang, Hui; Hu, Ke; Zhang, Dan-Wei; Li, Zhan-Ting; RSC Medicinal Chemistry  (2023) –; doi:10.1039/D2MD00463A

data_7246291
_publ_section_title
;
 Host--guest binding of tetracationic cyclophanes to photodynamic agents
 inhibits posttreatment phototoxicity and maintains antitumour efficacy
;
_journal_name_full               'RSC Medicinal Chemistry'
_journal_paper_doi               10.1039/D2MD00463A
_journal_year                    2023
_chemical_formula_moiety
'C56 H44 N4, C5 H9 N O, 3.25(Cl), Cl0.47 O0.28, Cl0.28 O0.72, 11(O)'
_chemical_formula_sum            'C61 H77 Cl4 N5 O13'
_chemical_formula_weight         1230.07
_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
_audit_creation_date             2022-08-01
_audit_creation_method
;
Olex2 1.3
(compiled Nov 21 2019 18:26:39 for OlexSys, GUI svn.r6003)
;
_audit_update_record
;
2022-08-04 deposited with the CCDC.	2023-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                69.309(2)
_cell_angle_beta                 85.526(2)
_cell_angle_gamma                72.745(2)
_cell_formula_units_Z            2
_cell_length_a                   10.8172(5)
_cell_length_b                   17.9640(7)
_cell_length_c                   18.8642(8)
_cell_measurement_reflns_used    9944
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      59.31
_cell_measurement_theta_min      3.72
_cell_volume                     3273.4(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      173.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            57588
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         58.499
_diffrn_reflns_theta_min         3.752
_exptl_absorpt_coefficient_mu    1.404
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.5573
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1467 before and 0.0650 after correction.
The Ratio of minimum to maximum transmission is 0.7415.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_description       block
_exptl_crystal_F_000             1300
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.585
_refine_diff_density_min         -0.706
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.572
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     804
_refine_ls_number_reflns         14038
_refine_ls_number_restraints     79
_refine_ls_restrained_S_all      1.576
_refine_ls_R_factor_all          0.1242
_refine_ls_R_factor_gt           0.1083
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3465
_refine_ls_wR_factor_ref         0.3685
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11063
_reflns_number_total             14038
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2md00463a2.cif
_cod_data_source_block           platon_sq_CCDC1
_cod_database_code               7246291
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.786
_shelx_estimated_absorpt_t_min   0.654
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C59-C60
 1.52 with sigma of 0.03
3. Uiso/Uaniso restraints and constraints
Uanis(Cl2) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl3') \\sim Ueq, Uanis(Cl4)
\\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(O14) \\sim Ueq, Uanis(Cl6) \\sim Ueq,
Uanis(O4) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O11) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O9) \\sim Ueq, Uanis(O5') \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(O9') \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Others
 Sof(Cl3')=1-FVAR(1)
 Sof(Cl3)=FVAR(1)
 Fixed Sof: Cl2(0.75) Cl4(0.5) Cl5(0.47) O14(0.28) Cl6(0.28) O4(0.72) O5(0.65)
 O5'(0.35) O9(0.5) O9'(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C28(H28A,H28B), C49(H49A,H49B), C56(H56A,H56B), C58(H58A,
 H58B), C59(H59A,H59B), C60(H60A,H60B)
5.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C13(H13), C14(H14),
 C15(H15), C16(H16), C17(H17), C19(H19), C20(H20), C23(H23), C24(H24), C26(H26),
  C27(H27), C29(H29), C30(H30), C32(H32), C33(H33), C36(H36), C37(H37),
 C38(H38), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C47(H47), C48(H48),
  C51(H51), C52(H52), C54(H54), C55(H55)
5.c Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C)
;
_shelx_res_checksum              82089
_shelx_fab_checksum              64431
_olex2_submission_special_instructions 'No special instructions were received'