Atomically Accurate Structural Tailoring of Thiacalix[4]arene-Protected Copper(II)-Based Metallamacrocycles
Liu, Chao; Mu, Wen-Lei; Wu, Linlin; Yu, Weidong; Yi, Xiao-Yi; Yan, Jun; Dalton Transactions  (2023) –; doi:10.1039/D3DT00455D

data_7712763
_publ_section_title
;
 Atomically Accurate Structural Tailoring of Thiacalix[4]arene-Protected
 Copper(II)-Based Metallamacrocycles
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00455D
_journal_year                    2023
_chemical_formula_moiety         'C156 H162 Cl3 Cu12 Na2 O32 P6 S12, 9[C3H7O]'
_chemical_formula_sum            'C183 H225 Cl3 Cu12 Na2 O41 P6 S12'
_chemical_formula_weight         4565.97
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-03-13
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2023-03-13 deposited with the CCDC.	2023-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                66.779(6)
_cell_angle_beta                 89.744(5)
_cell_angle_gamma                77.581(6)
_cell_formula_units_Z            2
_cell_length_a                   17.190(3)
_cell_length_b                   25.858(6)
_cell_length_c                   28.437(6)
_cell_measurement_reflns_used    9830
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      50.13
_cell_measurement_theta_min      4.42
_cell_volume                     11299(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.966
_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  0.0955
_diffrn_reflns_av_unetI/netI     0.1725
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            70690
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        51.438
_diffrn_reflns_theta_max         51.438
_diffrn_reflns_theta_min         4.150
_diffrn_source_current           2.86
_diffrn_source_power             0.1997996
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.506
_exptl_absorpt_correction_T_max  0.7501
_exptl_absorpt_correction_T_min  0.4015
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1645 before and 0.0777 after correction.
The Ratio of minimum to maximum transmission is 0.5353.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       block
_exptl_crystal_F_000             4708
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.631
_refine_diff_density_min         -0.886
_refine_diff_density_rms         0.119
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.973
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1979
_refine_ls_number_reflns         36208
_refine_ls_number_restraints     592
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.1721
_refine_ls_R_factor_gt           0.1116
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1955P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3018
_refine_ls_wR_factor_ref         0.3459
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16578
_reflns_number_total             36208
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00455d2.cif
_cod_data_source_block           Cu12L3
_cod_database_code               7712763
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.212
_shelx_estimated_absorpt_t_min   0.117
_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
 C62-C124
 1.55 with sigma of 0.01
 H03E-H58C
 2 with sigma of 0.01
 H11R-H18
 2 with sigma of 0.01
 C111-C58
 2.5 with sigma of 0.01
 C55-C58
 1.55 with sigma of 0.01
 C55-C111
 1.55 with sigma of 0.01
 C124-C73
 1.55 with sigma of 0.01
 C61-C59
 2.2 with sigma of 0.01
 C58-C111
 2.2 with sigma of 0.01
 C80-C100
 1.45 with sigma of 0.01
 H28-H79C
 2 with sigma of 0.01
 H11M-H11P
 2 with sigma of 0.01
 C76-C24
 1.5 with sigma of 0.01
 C76-C75
 1.5 with sigma of 0.01
 C76-C125
 1.5 with sigma of 0.01
 P0K-O2 \\sim P0K-O2A
 with sigma of 0.04
 Cu6-O2 \\sim Cu6-O2A
 with sigma of 0.04
 Na2-O2 \\sim Na2-O2A
 with sigma of 0.04
3. Rigid bond restraints
 C84, C85, C86, C98, C57, C60
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C59, C61, C62, C124
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C24, C76
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C55, C58
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C04G, C77
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C112, C108
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 P0K, C84
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C56, C55
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C52, C53
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C04G, C05H
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C02O, C026
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C55, C81
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C88, C89
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C23, C24
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C27, C100
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C76, C75
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C76, C113
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C76, C125
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C55 \\sim C111 \\sim C56 \\sim C58: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Cu8 \\sim Cl3: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C41 \\sim C109 \\sim C110 \\sim C119 \\sim C5 \\sim C6: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C124 \\sim C61 \\sim C62 \\sim C59: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C108 \\sim C115 \\sim C112 \\sim C114: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C120 \\sim C121 \\sim C122 \\sim C123: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.01 within 2A
C65 \\sim C68 \\sim C67 \\sim C66: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C1 \\sim C2 \\sim C3 \\sim C4: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C76 \\sim C75 \\sim C125 \\sim C113: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(O2) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C98) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C85) \\sim Ueq,
Uanis(C107) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C96)
\\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C120) \\sim Ueq,
Uanis(C121) \\sim Ueq, Uanis(C122) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C59)
\\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(C76) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C99)
\\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C92) \\sim Ueq,
Uanis(C93) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C109)
\\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C119) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C6) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C78)
\\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C81) \\sim Ueq,
Uanis(C55) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C102)
\\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C100) \\sim Ueq, Uanis(O7) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3)
\\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C103) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C77)
\\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C124) \\sim Ueq, Uanis(C62) \\sim Ueq,
Uanis(C59) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C75) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: O2(0.5) O2A(0.5)
6.a Riding coordinates:
 C51(H51A,H51B,H51C), C48(H48A,H48B,H48C), C115(H11A,H11B,H11C), C112(H11D,
 H11E,H11F), C53(H53A,H53B,H53C), C78(H78A,H78B,H78C), C59(H59A,H59B,H59C),
 C120(H12A,H12B,H12C), C121(H12D,H12E,H12F), C66(H66A,H66B,H66C), C118(H11P,
 H11Q,H11R), C113(H11S,H11T,H11U), C75(H75A,H75B,H75C), C125(H12J,H12K,H12L)
6.b Aromatic/amide H refined with riding coordinates:
 C97(H97), C02A(H02A), C02F(H02F), C14(H14), C40(H40), C02R(H02R), C28(H28),
 C02X(H02X), C72(H72), C7(H7), C103(H103), C03D(H03D), C03E(H03E), C26(H26),
 C03G(H03G), C23(H23), C74(H74), C19(H19), C34(H34), C105(H105), C69(H69),
 C109(H109), C110(H110), C119(H119), C5(H5), C6(H6), C83(H83), C85(H85),
 C86(H86), C98(H98), C57(H57), C60(H60), C45(H45), C028(H028), C29(H29),
 C106(H106), C102(H102), C101(H101), C54(H54), C37(H37), C034(H034), C18(H18),
 C10(H10), C33(H33), C82(H82), C87(H87), C96(H96), C89(H89), C88(H88), C91(H91),
  C92(H92), C93(H93), C94(H94), C95(H95)
6.c Fitted hexagon refined as free rotating group:
 C109(C110,C119,C5,C6,C41), C84(C85,C86,C98,C57,C60), C29(C104,C106,C102,C101,
 C54), C107(C82,C87,C96,C89,C88), C90(C91,C92,C93,C94,C95)
6.d Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C), C50(H50A,H50B,H50C), C49(H49A,H49B,H49C), C05H(H05A,H05B,
 H05C), C114(H11G,H11H,H11I), C68(H68A,H68B,H68C), C56(H56A,H56B,H56C),
 C111(H11J,H11K,H11L), C77(H77A,H77B,H77C), C79(H79A,H79B,H79C), C80(H80A,H80B,
 H80C), C122(H12G,H12H,H12I), C117(H11M,H11N,H11O), C052(H05D,H05E,H05F),
 C99(H99A,H99B,H99C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C4(H4A,H4B,H4C),
  C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C67(H67A,H67B,H67C), C58(H58A,H58B,H58C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 408 electrons were found in a volume of 1792\%A^3^ in 1 void per unit cell. This is consistent with the presence of 5[C3H7ON] per Asymmetric Unit which account for 400 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              83133
_shelx_fab_checksum              57672
_olex2_submission_special_instructions 'No special instructions were received'