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_1566753
_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
'C100 H104 N4 O8 Rh4, 4(C F3 O3 S), 3.5[CH3OH], 1[C6H14O]'
_chemical_formula_sum            'C113.5 H132 F12 N4 O24.5 Rh4 S4'
_chemical_formula_weight         2712.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-09-07
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6394)
;
_audit_update_record
;
2022-01-06 deposited with the CCDC.	2022-04-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.273(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.5383(4)
_cell_length_b                   19.2201(5)
_cell_length_c                   41.5739(12)
_cell_measurement_reflns_used    9782
_cell_measurement_temperature    173.00
_cell_measurement_theta_max      50.898
_cell_measurement_theta_min      3.268
_cell_volume                     12381.4(6)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      173.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0664
_diffrn_reflns_av_unetI/netI     0.0697
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            158418
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.724
_diffrn_reflns_theta_min         1.474
_exptl_absorpt_coefficient_mu    0.677
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.6270
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1332 before and 0.0715 after correction.
The Ratio of minimum to maximum transmission is 0.8351.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_description       block
_exptl_crystal_F_000             5556
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         2.624
_refine_diff_density_min         -0.681
_refine_diff_density_rms         0.114
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.26(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2617
_refine_ls_number_reflns         46905
_refine_ls_number_restraints     7618
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.1100
_refine_ls_R_factor_gt           0.0834
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1721P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2272
_refine_ls_wR_factor_ref         0.2525
_reflns_Friedel_coverage         0.930
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                32209
_reflns_number_total             46905
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00437b2.cif
_cod_data_source_block           2
_cod_original_formula_sum        'C113.50 H132 F12 N4 O24.50 Rh4 S4'
_cod_database_code               1566753
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.929
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.74(4)
 0.26(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 S6-C45
 1.7 with sigma of 0.02
 Rh7-C39
 2.9 with sigma of 0.02
 C155-Rh7
 2.9 with sigma of 0.02
 C205-C91 = C181-C103
 1.53 with sigma of 0.02
 C195-C135 = C203-C17 = C51-C137 = C49-C67
 1.53 with sigma of 0.02
 C103-C91
 2.65 with sigma of 0.02
 C81-C115 = C97-C57 = C5-C59 = C187-C117 = C29-C193
 1.53 with sigma of 0.02
 C103-C185
 2.65 with sigma of 0.02
 C49-C69
 2.65 with sigma of 0.02
 C51-C137 = C203-C17
 1.53 with sigma of 0.02
 C193-C117
 2.65 with sigma of 0.02
 C49-C135
 2.65 with sigma of 0.02
 C193-C115
 2.65 with sigma of 0.02
 C195-C67
 2.65 with sigma of 0.02
 S5-C197 = S4-C188
 1.7 with sigma of 0.02
 C195-C17
 2.65 with sigma of 0.02
 S5-C197
 1.7 with sigma of 0.02
 C203-C137
 2.65 with sigma of 0.02
 F11-C197 = F13-C197 = F2-C197 = F1-C188 = F4-C188 = F10-C188
 1.3 with sigma of 0.02
 C203-C135
 2.65 with sigma of 0.02
 S7-O35 = S7-O37 = S7-O9
 1.41 with sigma of 0.02
 F19-C99 = F5-C99 = F21-C99
 1.31 with sigma of 0.02
 S7-C99
 1.7 with sigma of 0.02
 F19-F21 = F21-F5
 2.1 with sigma of 0.02
 O35-O9
 2.4 with sigma of 0.02
 F5-F19
 2.1 with sigma of 0.02
 O35-O37 = O37-O9
 2.4 with sigma of 0.02
 O35-C99
 2.5 with sigma of 0.02
 O9-C99
 2.5 with sigma of 0.02
 O37-C99
 2.5 with sigma of 0.02
 S2-C191
 1.7 with sigma of 0.02
 C191-O3
 2.5 with sigma of 0.02
 C191-O27
 2.5 with sigma of 0.02
 O29-C191
 2.5 with sigma of 0.02
 F9-F15 = F17-F9
 2.1 with sigma of 0.02
 F15-F17
 2.1 with sigma of 0.02
 F9-C191 = F15-C191 = F17-C191
 1.31 with sigma of 0.02
 F13-F11
 2.1 with sigma of 0.02
 F13-F2 = F2-F11
 2.1 with sigma of 0.02
 S3-O17 = S3-O31 = S3-O33
 1.43 with sigma of 0.02
 F7-C3 = F23-C3 = F24-C3
 1.31 with sigma of 0.02
 O17-O33
 2.5 with sigma of 0.02
 F23-F24
 2.1 with sigma of 0.02
 F23-F7 = F7-F24
 2.1 with sigma of 0.02
 O17-O31 = O31-O33
 2.5 with sigma of 0.02
 S7-F5
 2.58 with sigma of 0.02
 O17-C3
 2.4 with sigma of 0.02
 O33-C3
 2.4 with sigma of 0.02
 F19-S7
 2.58 with sigma of 0.02
 F7-S3
 2.58 with sigma of 0.02
 F21-S7
 2.58 with sigma of 0.02
 O31-C3
 2.4 with sigma of 0.02
 F23-S3
 2.58 with sigma of 0.02
 F24-S3
 2.58 with sigma of 0.02
 S8-C199
 1.7 with sigma of 0.02
 S8-O38 = S8-O19 = S8-O13
 1.43 with sigma of 0.02
 F14-C199 = F18-C199 = F16-C199
 1.3 with sigma of 0.02
 S8-O13 = S8-O19 = S8-O38
 1.31 with sigma of 0.02
 S8-F14
 2.58 with sigma of 0.02
 O13-C199
 2.4 with sigma of 0.02
 O19-C199
 2.4 with sigma of 0.02
 S8-F16
 2.58 with sigma of 0.02
 O38-C199
 2.4 with sigma of 0.02
 F18-S8
 2.58 with sigma of 0.02
 C19-Rh3
 2.9 with sigma of 0.02
 C153-Rh3
 2.9 with sigma of 0.02
 O7-C19 = O25-C153 = O15-C155 = O39-C39
 1.3 with sigma of 0.02
 Rh3-O25 = Rh3-O7
 2 with sigma of 0.02
 S5-F13
 2.58 with sigma of 0.02
 S5-F2
 2.58 with sigma of 0.02
 S5-F11
 2.58 with sigma of 0.02
 O5-C197
 2.4 with sigma of 0.02
 O2-C197
 2.4 with sigma of 0.02
 O21-C197
 2.4 with sigma of 0.02
 F12-C25 = F8-C25 = F6-C25
 1.3 with sigma of 0.02
 S1-C25
 1.7 with sigma of 0.02
 S3-C3
 1.7 with sigma of 0.01
 C205-C181
 2.65 with sigma of 0.02
 C205-C183
 2.65 with sigma of 0.02
 C81-C57
 2.65 with sigma of 0.02
 C187-C29
 2.65 with sigma of 0.02
 C97-C115
 2.65 with sigma of 0.02
 C5-C117
 2.65 with sigma of 0.02
 C81-C29
 2.65 with sigma of 0.02
 C5-C57
 2.65 with sigma of 0.02
 C97-C59
 2.65 with sigma of 0.02
 C187-C59
 2.65 with sigma of 0.02
 C51-C17
 2.65 with sigma of 0.02
 C51-C69
 2.65 with sigma of 0.02
 O13-O38 = O38-O19
 2.4 with sigma of 0.02
 O19-O13
 2.4 with sigma of 0.02
 C204-C36
 2.65 with sigma of 0.02
 C204-C128
 2.65 with sigma of 0.02
 C204-C180 = C163-C128 = C121-C146 = C208-C148 = C55-C36
 1.53 with sigma of 0.02
 C207-C67
 2.65 with sigma of 0.02
 C207-C137
 2.65 with sigma of 0.02
 C207-C69
 1.53 with sigma of 0.02
 C38-C76 = C33-C78 = C72-C182 = C149-C70 = C143-C133 = C9-C47 = C79-C141 =
 C179-C35 = C31-C52 = C53-C62 = C107-C64 = C132-C20 = C206-C194 = C156-C48 =
 C164-C40 = C159-C198
 1.53 with sigma of 0.02
 H13C-H47B
 2.1 with sigma of 0.02
 Rh7-O15
 1.95 with sigma of 0.02
 O15-C39
 2.3 with sigma of 0.02
 O39-C155
 2.3 with sigma of 0.02
 C67-Rh7
 2.1 with sigma of 0.02
 O39-O15
 2.6 with sigma of 0.02
 Rh7-C69
 2.1 with sigma of 0.02
 Rh7-O39 = Rh9-O39 = Rh7-O15 = Rh9-O15
 2 with sigma of 0.02
 Rh7-C135 = Rh7-C17 = Rh7-C137
 2.1 with sigma of 0.02
 Rh9-C135 = Rh9-C67 = Rh9-C69 = Rh9-C17 = Rh9-C137
 2 with sigma of 0.02
 C2-C165
 1.53 with sigma of 0.02
 Rh7-O39 \\sim Rh9-O39
 with sigma of 0.02
4. 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
5. 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
6. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
7. Others
 Sof(Rh9)=1-FVAR(1)
 Sof(Rh7)=FVAR(1)
8.a Me refined with riding coordinates:
 C2(H2A,H2B,H2C), C95(H95A,H95B,H95C), C193(H19A,H19B,H19C), C195(H19D,H19E,
 H19F), C49(H49A,H49B,H49C), C203(H20A,H20B,H20C), C103(H10D,H10E,H10F)
8.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10), C16(H16), C24(H24), C30(H30), C42(H42), C44(H44), C58(H58),
 C60(H60), C66(H66), C82(H82), C84(H84), C88(H88), C90(H90), C100(H100),
 C116(H116), C122(H122), C136(H136), C150(H150), C154(H154), C162(H162),
 C166(H166), C168(H168), C170(H170), C172(H172), C176(H176), C178(H178),
 C186(H186), C105(H105), C61(H61), C123(H123), C147(H147), C37(H37), C75(H75),
 C77(H77), C157(H157), C173(H173), C87(H87), C11(H11), C177(H177)
8.c Fitted pentagon refined as free rotating group:
 C57(C115,C29,C117,C59), C67(C135,C17,C137,C69), C41(C165,C83,C167,C21),
 C181(C91,C183,C23,C185)
8.d Fitted hexagon refined as free rotating group:
 C68(C70,C72,C74,C76,C78), N5(C82,C84,C86,C88,C90), N3(C170,C172,C174,C176,
 C178), C139(C35,C141,C71,C143,C9), C19(C153,C77,C155,C39,C157), N7(C173,C87,
 C175,C11,C177)
8.e Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C130(H13D,H13E,H13F), C132(H13G,H13H,H13I), C138(H13J,
 H13K,H13L), C152(H15D,H15E,H15F), C156(H15G,H15H,H15I), C158(H15J,H15K,H15L),
 C160(H16A,H16B,H16C), C164(H16D,H16E,H16F), C182(H18A,H18B,H18C), C192(H19G,
 H19H,H19I), C202(H20J,H20K,H20L), C204(H20M,H20N,H20O), C206(H20P,H20Q,H20R),
 C208(H20S,H20T,H20U), C53(H53A,H53B,H53C), C107(H10G,H10H,H10I), C55(H55A,H55B,
 H55C), C113(H11A,H11B,H11C), C121(H12A,H12B,H12C), C31(H31A,H31B,H31C),
 C63(H63A,H63B,H63C), C129(H12D,H12E,H12F), C65(H65A,H65B,H65C), C33(H33A,H33B,
 H33C), C133(H13A,H13B,H13C), C73(H73A,H73B,H73C), C149(H14A,H14B,H14C),
 C151(H15A,H15B,H15C), C79(H79A,H79B,H79C), C159(H15M,H15N,H15O), C5(H5A,H5B,
 H5C), C161(H16G,H16H,H16I), C81(H81A,H81B,H81C), C163(H16J,H16K,H16L),
 C169(H16M,H16N,H16O), C85(H85A,H85B,H85C), C171(H17A,H17B,H17C), C43(H43A,H43B,
 H43C), C179(H17D,H17E,H17F), C93(H93A,H93B,H93C), C187(H18D,H18E,H18F),
 C47(H47A,H47B,H47C), C189(H18G,H18H,H18I), C97(H97A,H97B,H97C), C101(H10A,H10B,
 H10C), C51(H51A,H51B,H51C), C205(H20D,H20E,H20F), C207(H20G,H20H,H20I)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 462 electrons were 
found in a volume of 2665\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
3.5[CH3OH], 1[C6H14O] per Asymmetric Unit 
which account for 484 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              25100
_shelx_hkl_checksum              50020
_shelx_fab_checksum              57194
_olex2_submission_special_instructions 'No special instructions were received'