ThC<sub>2</sub>@C<sub>82</sub> <i>versus</i> Th@C<sub>84</sub>: unexpected formation of triangular thorium carbide cluster inside fullerenes.
Shen, Yi; Yu, Xiaojuan; Meng, Qingyu; Yao, Yang-Rong; Autschbach, Jochen; Chen, Ning; Chemical science 13 (2022) 12980–12986; doi:10.1039/d2sc04846a

data_1567901
_publ_section_title
;
 ThC<sub>2</sub>@C<sub>82</sub> <i>versus</i> Th@C<sub>84</sub>:
 unexpected formation of triangular thorium carbide cluster inside
 fullerenes.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              12980
_journal_page_last               12986
_journal_paper_doi               10.1039/d2sc04846a
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         '0.5(C164), C2 Th1, C36 H44 N4 Ni, 2(C6 H6)'
_chemical_formula_sum            'C132 H56 N4 Ni Th'
_chemical_formula_weight         1988.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-07-05 deposited with the CCDC.	2022-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.325(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.3169(18)
_cell_length_b                   15.0051(11)
_cell_length_c                   19.9071(15)
_cell_measurement_reflns_used    9876
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      55.27
_cell_measurement_theta_min      3.05
_cell_volume                     7540.8(10)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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      120.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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  0.0813
_diffrn_reflns_av_unetI/netI     0.0504
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            86315
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         56.567
_diffrn_reflns_theta_min         3.046
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.943
_exptl_absorpt_correction_T_max  0.612
_exptl_absorpt_correction_T_min  0.515
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1286 before and 0.0835 after correction. The Ratio of minimum to maximum transmission is 0.6929. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear dark black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.752
_exptl_crystal_description       block
_exptl_crystal_F_000             3976
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.885
_refine_diff_density_min         -0.679
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1064
_refine_ls_number_reflns         7836
_refine_ls_number_restraints     1484
_refine_ls_restrained_S_all      1.127
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0567
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0674P)^2^+47.5168P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1366
_refine_ls_wR_factor_ref         0.1474
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6330
_reflns_number_total             7836
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04846a2.cif
_cod_data_source_block           thc2@cs(6)-c82
_cod_depositor_comments
'Adding full bibliography for 1567901--1567902.cif.'
_cod_database_code               1567901
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.648
_shelx_estimated_absorpt_t_min   0.536
_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
 C46-C47 = C56-C57 = C59-C60 = C65-C66 = C71-C72
 1.4 with sigma of 0.01
 C7S-C8S \\sim C8S-C9S \\sim C9S-C10S \\sim C10S-C11S \\sim C11S-C12S \\sim
C12S-C7S
 with sigma of 0.02
 C7S-C9S \\sim C7S-C11S \\sim C8S-C10S \\sim C8S-C12S \\sim C10S-C12S \\sim
C9S-C11S
 with sigma of 0.02
 C60-C61 \\sim C61-C62 \\sim C62-C38 \\sim C38-C37 \\sim C37-C60
 with sigma of 0.02
 C60-C62 \\sim C60-C38 \\sim C61-C38 \\sim C61-C37 \\sim C62-C37
 with sigma of 0.02
 C59-C58 \\sim C58-C57 \\sim C57-C75 \\sim C75-C76 \\sim C76-C59
 with sigma of 0.02
 C59-C57 \\sim C59-C75 \\sim C58-C75 \\sim C58-C76 \\sim C57-C76
 with sigma of 0.02
 C81-C70 \\sim C70-C71 \\sim C71-C73 \\sim C73-C82 \\sim C82-C81
 with sigma of 0.02
 C81-C71 \\sim C81-C73 \\sim C70-C73 \\sim C70-C82 \\sim C71-C82
 with sigma of 0.02
 C45-C66 \\sim C66-C67 \\sim C67-C68 \\sim C68-C46 \\sim C46-C45
 with sigma of 0.02
 C45-C67 \\sim C45-C68 \\sim C66-C68 \\sim C66-C46 \\sim C67-C46
 with sigma of 0.02
 C72-C53 \\sim C53-C52 \\sim C52-C51 \\sim C51-C50 \\sim C50-C72
 with sigma of 0.02
 C72-C52 \\sim C72-C51 \\sim C53-C51 \\sim C53-C50 \\sim C52-C50
 with sigma of 0.02
 C64-C65 \\sim C65-C42 \\sim C42-C41 \\sim C41-C63 \\sim C63-C64
 with sigma of 0.02
 C64-C42 \\sim C64-C41 \\sim C65-C41 \\sim C65-C63 \\sim C42-C63
 with sigma of 0.02
 C9-C28 \\sim C28-C29 \\sim C29-C11 \\sim C11-C10 \\sim C10-C9
 with sigma of 0.02
 C9-C29 \\sim C9-C11 \\sim C28-C11 \\sim C28-C10 \\sim C29-C10
 with sigma of 0.02
 C33-C32 \\sim C32-C31 \\sim C31-C55 \\sim C55-C56 \\sim C56-C33
 with sigma of 0.02
 C33-C31 \\sim C33-C55 \\sim C32-C55 \\sim C32-C56 \\sim C31-C56
 with sigma of 0.02
 C5-C21 \\sim C21-C22 \\sim C22-C7 \\sim C7-C6 \\sim C6-C5
 with sigma of 0.02
 C5-C22 \\sim C5-C7 \\sim C21-C7 \\sim C21-C6 \\sim C22-C6
 with sigma of 0.02
 C13-C14 \\sim C14-C15 \\sim C15-C3 \\sim C3-C2 \\sim C2-C13
 with sigma of 0.02
 C13-C15 \\sim C13-C3 \\sim C14-C3 \\sim C14-C2 \\sim C15-C2
 with sigma of 0.02
 C47-C48 \\sim C48-C26 \\sim C26-C25 \\sim C25-C24 \\sim C24-C47
 with sigma of 0.02
 C47-C26 \\sim C47-C25 \\sim C48-C25 \\sim C48-C24 \\sim C26-C24
 with sigma of 0.02
 C39-C40 \\sim C40-C19 \\sim C19-C18 \\sim C18-C17 \\sim C17-C39
 with sigma of 0.02
 C39-C19 \\sim C39-C18 \\sim C40-C18 \\sim C40-C17 \\sim C19-C17
 with sigma of 0.02
 C38-C39 \\sim C39-C40 \\sim C40-C41 \\sim C41-C63 \\sim C63-C62 \\sim C62-C38
 with sigma of 0.02
 C38-C40 \\sim C38-C63 \\sim C39-C41 \\sim C39-C62 \\sim C41-C62 \\sim C40-C63
 with sigma of 0.02
 C46-C48 \\sim C46-C24 \\sim C47-C45 \\sim C47-C68
 with sigma of 0.02
 C56-C58 \\sim C56-C75 \\sim C57-C55 \\sim C57-C33
 with sigma of 0.02
 C59-C61 \\sim C59-C37 \\sim C60-C58 \\sim C60-C76
 with sigma of 0.02
 C65-C67 \\sim C65-C45 \\sim C66-C64 \\sim C66-C42
 with sigma of 0.02
 C71-C50 \\sim C71-C53 \\sim C72-C70 \\sim C72-C73
 with sigma of 0.02
 C1-C2 \\sim C1-C6 \\sim C1-C10
 with sigma of 0.02
 C2-C6 \\sim C6-C10 \\sim C10-C2
 with sigma of 0.02
 C4-C3 \\sim C4-C5 \\sim C4-C18
 with sigma of 0.02
 C3-C5 \\sim C5-C18 \\sim C18-C3
 with sigma of 0.02
 C8-C7 \\sim C8-C9 \\sim C8-C25
 with sigma of 0.02
 C7-C9 \\sim C9-C25 \\sim C25-C7
 with sigma of 0.02
 C12-C11 \\sim C12-C13 \\sim C12-C32
 with sigma of 0.02
 C11-C13 \\sim C13-C32 \\sim C32-C11
 with sigma of 0.02
 C16-C15 \\sim C16-C17 \\sim C16-C36
 with sigma of 0.02
 C15-C17 \\sim C17-C36 \\sim C36-C15
 with sigma of 0.02
 C20-C19 \\sim C20-C21 \\sim C20-C43
 with sigma of 0.02
 C19-C21 \\sim C21-C43 \\sim C43-C19
 with sigma of 0.02
 C23-C22 \\sim C23-C24 \\sim C23-C44
 with sigma of 0.02
 C22-C24 \\sim C24-C44 \\sim C44-C22
 with sigma of 0.02
 C27-C26 \\sim C27-C28 \\sim C27-C51
 with sigma of 0.02
 C26-C28 \\sim C28-C51 \\sim C51-C26
 with sigma of 0.02
 C30-C29 \\sim C30-C31 \\sim C30-C52
 with sigma of 0.02
 C29-C31 \\sim C31-C52 \\sim C52-C29
 with sigma of 0.02
 C34-C33 \\sim C34-C35 \\sim C34-C14
 with sigma of 0.02
 C33-C35 \\sim C35-C14 \\sim C14-C33
 with sigma of 0.02
 C35-C34 \\sim C35-C36 \\sim C35-C58
 with sigma of 0.02
 C34-C36 \\sim C36-C58 \\sim C58-C34
 with sigma of 0.02
 C36-C35 \\sim C36-C37 \\sim C36-C16
 with sigma of 0.02
 C35-C37 \\sim C37-C16 \\sim C16-C35
 with sigma of 0.02
 C43-C42 \\sim C43-C44 \\sim C43-C20
 with sigma of 0.02
 C42-C44 \\sim C44-C20 \\sim C20-C42
 with sigma of 0.02
 C44-C43 \\sim C44-C45 \\sim C44-C23
 with sigma of 0.02
 C43-C45 \\sim C45-C23 \\sim C23-C43
 with sigma of 0.02
 C49-C50 \\sim C49-C48 \\sim C49-C69
 with sigma of 0.02
 C48-C50 \\sim C50-C69 \\sim C69-C48
 with sigma of 0.02
 C54-C53 \\sim C54-C55 \\sim C54-C74
 with sigma of 0.02
 C53-C55 \\sim C55-C74 \\sim C74-C53
 with sigma of 0.02
 C69-C68 \\sim C69-C70 \\sim C69-C49
 with sigma of 0.02
 C68-C70 \\sim C70-C49 \\sim C49-C68
 with sigma of 0.02
 C74-C73 \\sim C74-C75 \\sim C74-C54
 with sigma of 0.02
 C73-C75 \\sim C75-C54 \\sim C54-C73
 with sigma of 0.02
 C77-C76 \\sim C77-C78 \\sim C77-C82
 with sigma of 0.02
 C76-C78 \\sim C78-C82 \\sim C82-C76
 with sigma of 0.02
 C78-C77 \\sim C78-C79 \\sim C78-C61
 with sigma of 0.02
 C77-C79 \\sim C79-C61 \\sim C61-C77
 with sigma of 0.02
 C79-C78 \\sim C79-C80 \\sim C79-C64
 with sigma of 0.02
 C78-C80 \\sim C80-C64 \\sim C64-C78
 with sigma of 0.02
 C80-C79 \\sim C80-C81 \\sim C80-C67
 with sigma of 0.02
 C79-C81 \\sim C81-C67 \\sim C67-C79
 with sigma of 0.02
3. Restrained planarity
 C37, C38, C60, C61, C62
 with sigma of 0.1
 C57, C58, C59, C75, C76
 with sigma of 0.1
 C70, C71, C73, C81, C82
 with sigma of 0.1
 C45, C46, C66, C67, C68
 with sigma of 0.1
 C50, C51, C52, C53, C72
 with sigma of 0.1
 C41, C42, C63, C64, C65
 with sigma of 0.1
 C9, C10, C11, C28, C29
 with sigma of 0.1
 C31, C32, C33, C55, C56
 with sigma of 0.1
 C5, C6, C7, C21, C22
 with sigma of 0.1
 C2, C3, C13, C14, C15
 with sigma of 0.1
 C24, C25, C26, C47, C48
 with sigma of 0.1
 C17, C18, C19, C39, C40
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Th1 \\sim Th2 \\sim Th3: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C7S \\sim C8S \\sim C9S \\sim C10S \\sim C11S \\sim C12S: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim 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 C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C84) \\sim Ueq, Uanis(C83) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Others
 1*[Sof(Th2)]+1*[Sof(Th1)]+1*[Sof(Th3)]=0.5 with esd of 0.00001
 Fixed Sof: C1(0.5) C2(0.5) C3(0.5) C4(0.5) C5(0.5) C6(0.5) C7(0.5) C8(0.5)
 C9(0.5) C10(0.5) C11(0.5) C12(0.5) C13(0.5) C14(0.5) C15(0.5) C16(0.5)
 C17(0.5) C18(0.5) C19(0.5) C20(0.5) C21(0.5) C22(0.5) C23(0.5) C24(0.5)
 C25(0.5) C26(0.5) C27(0.5) C28(0.5) C29(0.5) C30(0.5) C31(0.5) C33(0.5)
 C34(0.5) C35(0.5) C36(0.5) C37(0.5) C38(0.5) C39(0.5) C40(0.5) C41(0.5)
 C42(0.5) C43(0.5) C44(0.5) C45(0.5) C46(0.5) C47(0.5) C48(0.5) C49(0.5)
 C50(0.5) C51(0.5) C53(0.5) C54(0.5) C55(0.5) C56(0.5) C57(0.5) C58(0.5)
 C59(0.5) C60(0.5) C61(0.5) C62(0.5) C63(0.5) C64(0.5) C65(0.5) C66(0.5)
 C67(0.5) C68(0.5) C69(0.5) C70(0.5) C71(0.5) C72(0.5) C73(0.5) C74(0.5)
 C75(0.5) C76(0.5) C77(0.5) C78(0.5) C79(0.5) C80(0.5) C81(0.5) C82(0.5)
 C83(0.5) C84(0.5) C7S(0.5) H7S(0.5) C8S(0.5) H8S(0.5) C9S(0.5) H9S(0.5)
 C10S(0.5) H10S(0.5) C11S(0.5) H11S(0.5) C12S(0.5) H12S(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C11P(H11A,H11B), C13P(H13A,H13B), C15P(H15A,H15B), C17P(H17A,H17B)
6.b Aromatic/amide H refined with riding coordinates:
 C3P(H3P), C8P(H8P), C1S(H1S), C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S),
 C6S(H6S), C7S(H7S), C8S(H8S), C9S(H9S), C10S(H10S), C11S(H11S), C12S(H12S)
6.c Idealised Me refined as rotating group:
 C12P(H12A,H12B,H12C), C14P(H14A,H14B,H14C), C16P(H16A,H16B,H16C), C18P(H18A,
 H18B,H18C)
;
_shelx_res_checksum              35514
_shelx_hkl_checksum              41217
_olex2_submission_special_instructions 'No special instructions were received'