Highly selective synthesis and near-infrared photothermal conversion of metalla-Borromean ring and [2]catenane assemblies
Dang, Li-Long; Li, Ting-Ting; Zhang, Ting-Ting; Zhao, Ying; Chen, Tian; Gao, Xiang; Ma, Lufang; Jin, Guo-Xin; Chemical Science  (2022) –; doi:10.1039/D2SC00437B

data_1566755
_publ_section_title
;
 Highly selective synthesis and near-infrared photothermal conversion of
 metalla-Borromean ring and [2]catenane assemblies
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00437B
_journal_year                    2022
_chemical_formula_moiety
'3(C108 H92 N8 O12 Rh4), C24 H42 O4 Rh2, 18[CF3SO3]'
_chemical_formula_sum            'C366 H318 F54 N24 O94 Rh14 S18'
_chemical_formula_weight         9600.25
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-01-15
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-01-17 deposited with the CCDC.	2022-04-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.086(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.474(5)
_cell_length_b                   34.090(9)
_cell_length_c                   38.801(10)
_cell_measurement_reflns_used    9171
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      51.81
_cell_measurement_theta_min      2.432
_cell_volume                     26148(12)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0699
_diffrn_reflns_av_unetI/netI     0.0776
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            137431
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.409
_diffrn_reflns_theta_min         2.248
_diffrn_source_current           2.86
_diffrn_source_power             0.19931339999999997
_diffrn_source_voltage           69.69
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.256
_exptl_absorpt_correction_T_max  0.7506
_exptl_absorpt_correction_T_min  0.5048
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1297 before and 0.0975 after correction.
The Ratio of minimum to maximum transmission is 0.6725.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.219
_exptl_crystal_description       block
_exptl_crystal_F_000             9676
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.383
_refine_diff_density_min         -1.370
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.146
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1793
_refine_ls_number_reflns         47779
_refine_ls_number_restraints     5532
_refine_ls_restrained_S_all      1.188
_refine_ls_R_factor_all          0.1552
_refine_ls_R_factor_gt           0.1024
_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^)+(0.0100P)^2^+70.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2124
_refine_ls_wR_factor_ref         0.2336
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21753
_reflns_number_total             47779
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00437b2.cif
_cod_data_source_block           p21c_CCDC1
_cod_original_cell_volume        26149(11)
_cod_database_code               1566755
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.562
_shelx_estimated_absorpt_t_min   0.521
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C164-C166 = C164-C162 = C162-C168
 1.39 with sigma of 0.02
 C167-C120
 2.65 with sigma of 0.02
 C17-C77
 2.65 with sigma of 0.02
 C159-C118 = C163-C116 = C21-C124 = C167-C122 = C141-C120
 1.53 with sigma of 0.02
 C167-C124
 2.65 with sigma of 0.02
 C162-C98
 2.39 with sigma of 0.02
 C123-C117 = C137-C113 = C39-C57 = C63-C115 = C61-C29 = C171-C77 = C17-C153 =
 C65-C19 = C35-C151 = C85-C75
 1.53 with sigma of 0.02
 C164-C100
 2.39 with sigma of 0.02
 C17-C19
 2.65 with sigma of 0.02
 C168-C164
 2.39 with sigma of 0.02
 C162-C166
 2.39 with sigma of 0.02
 C157-C101
 2.65 with sigma of 0.02
 C69-C51
 2.65 with sigma of 0.02
 C169-C13
 2.65 with sigma of 0.02
 C71-C67
 2.65 with sigma of 0.02
 C139-C25
 2.65 with sigma of 0.02
 C2-C67 = C71-C133 = C143-C33 = C81-C131 = C5-C135 = C161-C51 = C69-C101 =
 C157-C25 = C139-C13 = C169-C103
 1.53 with sigma of 0.02
 C161-C103
 2.65 with sigma of 0.02
 C143-C133
 2.65 with sigma of 0.02
 C71-C33
 2.65 with sigma of 0.02
 C143-C131
 2.65 with sigma of 0.02
 C161-C101
 2.65 with sigma of 0.02
 C81-C33
 2.65 with sigma of 0.02
 C69-C25
 2.65 with sigma of 0.02
 C81-C135
 2.65 with sigma of 0.02
 C157-C13
 2.65 with sigma of 0.02
 C5-C131
 2.65 with sigma of 0.02
 C139-C103
 2.65 with sigma of 0.02
 C5-C67
 2.65 with sigma of 0.02
 C169-C51
 2.65 with sigma of 0.02
 C2-C135
 2.65 with sigma of 0.02
 C2-C133
 2.65 with sigma of 0.02
 C171-C75
 2.65 with sigma of 0.02
 C35-C19
 2.65 with sigma of 0.02
 C137-C117
 2.65 with sigma of 0.02
 C65-C153
 2.65 with sigma of 0.02
 C39-C113
 2.65 with sigma of 0.02
 C85-C151
 2.65 with sigma of 0.02
 C39-C115
 2.65 with sigma of 0.02
 C137-C57
 2.65 with sigma of 0.02
 C63-C57
 2.65 with sigma of 0.02
 C171-C153
 2.65 with sigma of 0.02
 C63-C29
 2.65 with sigma of 0.02
 C61-C115
 2.65 with sigma of 0.02
 C65-C151
 2.65 with sigma of 0.02
 C61-C117
 2.65 with sigma of 0.02
 C35-C75
 2.65 with sigma of 0.02
 C123-C29
 2.65 with sigma of 0.02
 C85-C77
 2.65 with sigma of 0.02
 C123-C113
 2.65 with sigma of 0.02
 C117-C137
 2.65 with sigma of 0.02
 C83-C73
 2.65 with sigma of 0.02
 C165-C73
 2.65 with sigma of 0.02
 C141-C118
 2.65 with sigma of 0.02
 C79-C147
 2.65 with sigma of 0.02
 C41-C147
 2.65 with sigma of 0.02
 C159-C116
 2.65 with sigma of 0.02
 C165-C149
 2.65 with sigma of 0.02
 C163-C124
 2.65 with sigma of 0.02
 C41-C145
 2.65 with sigma of 0.02
 C122-C21
 2.65 with sigma of 0.02
 C83-C37
 2.65 with sigma of 0.02
 C83-C147 = C41-C73 = C79-C37 = C155-C149
 1.53 with sigma of 0.02
 C165-C145
 1.53 with sigma of 0.02
 C163-C118
 2.65 with sigma of 0.02
 C21-C116
 2.65 with sigma of 0.02
 C79-C149
 2.65 with sigma of 0.02
 C141-C122
 2.65 with sigma of 0.02
 C155-C37
 2.65 with sigma of 0.02
 C159-C120
 2.65 with sigma of 0.02
 C155-C145
 2.65 with sigma of 0.02
 C127-C55
 2.65 with sigma of 0.02
 C125-C27
 2.65 with sigma of 0.02
 C31-C109
 2.65 with sigma of 0.02
 C129-C53
 2.65 with sigma of 0.02
 C31-C107
 2.65 with sigma of 0.02
 C9-C107
 2.65 with sigma of 0.02
 C127-C27
 2.65 with sigma of 0.02
 C125-C53
 2.65 with sigma of 0.02
 C129-C109
 2.65 with sigma of 0.02
 C129-C55 = C127-C109 = C27-C31 = C125-C107 = C9-C53
 1.53 with sigma of 0.02
 C9-C55
 2.65 with sigma of 0.02
 O9-C43 = O19-C173
 1.43 with sigma of 0.02
 C173_$1-Rh3
 3.3 with sigma of 0.02
 C173_$1-Rh3_$1
 3.2 with sigma of 0.02
 H12J-H17G_$1
 2 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Me refined with riding coordinates:
 C17(H17A,H17B,H17C), C167(H16G,H16H,H16I), C173(H17G,H17H,H17I)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C8(H8), C10(H10), C16(H16), C18(H18), C22(H22), C24(H24),
 C30(H30), C32(H32), C34(H34), C38(H38), C40(H40), C42(H42), C44(H44), C48(H48),
  C50(H50), C70(H70), C72(H72), C76(H76), C78(H78), C82(H82), C92(H92),
 C94(H94), C104(H104), C114(H114), C132(H132), C136(H136), C138(H138),
 C146(H146), C148(H148), C152(H152), C154(H154), C160(H160), C162(H162),
 C164(H164), C87(H87), C45(H45), C23(H23), C3(H3), C97(H97), C49(H49), C99(H99),
  C111(H111), C7(H7), C59(H59), C119(H119), C15(H15)
6.c Fitted pentagon refined as free rotating group:
 C116(C118,C120,C122,C124), C25(C101,C51,C103,C13), C53(C107,C27,C109,C55),
 C113(C57,C115,C29,C117), C131(C33,C133,C67,C135), C145(C73,C147,C37,C149),
 C75(C151,C19,C153,C77)
6.d Fitted hexagon refined as free rotating group:
 N4(C1,C4,C6,C8,C10), N12(C16,C18,C20,C22,C24), N2(C32,C34,C36,C38,C40),
 N9(C42,C44,C46,C48,C50), C68(C70,C72,C74,C76,C78), C82(C84,C86,C88,C90,C92),
 C94(C96,C98,C100,C102,C104), C144(C146,C148,C150,C152,C154)
6.e Idealised Me refined as rotating group:
 C61(H61A,H61B,H61C), C123(H12A,H12B,H12C), C31(H31A,H31B,H31C), C125(H12D,
 H12E,H12F), C63(H63A,H63B,H63C), C127(H12G,H12H,H12I), C2(H2A,H2B,H2C),
 C129(H12J,H12K,H12L), C65(H65A,H65B,H65C), C137(H13A,H13B,H13C), C69(H69A,H69B,
 H69C), C139(H13D,H13E,H13F), C35(H35A,H35B,H35C), C141(H14A,H14B,H14C),
 C71(H71A,H71B,H71C), C143(H14D,H14E,H14F), C9(H9A,H9B,H9C), C155(H15A,H15B,
 H15C), C39(H39A,H39B,H39C), C157(H15G,H15H,H15I), C79(H79A,H79B,H79C),
 C159(H15D,H15E,H15F), C5(H5A,H5B,H5C), C161(H16J,H16K,H16L), C81(H81A,H81B,
 H81C), C163(H16A,H16B,H16C), C41(H41A,H41B,H41C), C165(H16D,H16E,H16F),
 C83(H83A,H83B,H83C), C21(H21A,H21B,H21C), C169(H16M,H16N,H16O), C85(H85A,H85B,
 H85C), C171(H17D,H17E,H17F), C43(H43A,H43B,H43C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 2548 electrons were 
found in a volume of 14290\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
9[CF3SO3] per Asymmetric Unit 
which account for 2628 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              7945
_shelx_hkl_checksum              35951
_shelx_fab_checksum              65765
_olex2_submission_special_instructions 'No special instructions were received'