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_7712765
_publ_section_title
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 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
'C208 H214 Cl4 Cu16 O40 P8 S16, 4(C3 H7 N O), 1[C3H7ON]'
_chemical_formula_sum            'C220 H242 Cl3.17 Cu16 N4 O44 P8 S16'
_chemical_formula_weight         5535.90
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-03-13
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-13 deposited with the CCDC.	2023-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.721(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.160(2)
_cell_length_b                   33.513(5)
_cell_length_c                   22.472(3)
_cell_measurement_reflns_used    9803
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      58.91
_cell_measurement_theta_min      2.87
_cell_volume                     12834(3)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_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 2013/2 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      150.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0772
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            152289
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         59.411
_diffrn_reflns_theta_min         2.869
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           2.86
_diffrn_source_power             0.19977099999999998
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.85
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.680
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.4497
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1577 before and 0.0756 after correction.
The Ratio of minimum to maximum transmission is 0.5983.
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    1.432
_exptl_crystal_description       block
_exptl_crystal_F_000             5672
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.545
_refine_diff_density_min         -1.160
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1502
_refine_ls_number_reflns         27914
_refine_ls_number_restraints     301
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0810
_refine_ls_R_factor_gt           0.0647
_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^)+(0.1247P)^2^+7.4782P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1920
_refine_ls_wR_factor_ref         0.2030
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21475
_reflns_number_total             27914
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00455d2.cif
_cod_data_source_block           Cu16L4
_cod_database_code               7712765
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.180
_shelx_estimated_absorpt_t_min   0.098
_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
 C6-C5
 1.4 with sigma of 0.01
 C4-C5
 1.4 with sigma of 0.01
 C3-C1
 1.4 with sigma of 0.01
 C9-C1
 1.4 with sigma of 0.01
 C7-C6
 1.4 with sigma of 0.01
 C3-C4
 1.4 with sigma of 0.01
 C8-C9
 1.4 with sigma of 0.01
 C1-C3 \\sim C1-C9
 with sigma of 0.02
 C85-C99 \\sim C86-C73
 with sigma of 0.04
 C89-C87 \\sim C89-C96
 with sigma of 0.04
 C89-C99 \\sim C89-C73
 with sigma of 0.02
 C89-C85 \\sim C89-C86
 with sigma of 0.04
 C85-C87 \\sim C86-C96
 with sigma of 0.04
 C87-C99 \\sim C96-C73
 with sigma of 0.04
 C1-C3 \\sim C2-C3
 with sigma of 0.02
 C1-C9 \\sim C2-C9
 with sigma of 0.04
 P00J-C1 \\sim P00J-C2
 with sigma of 0.04
 C1-C74 \\sim C2-C74
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O1 \\sim N1 \\sim C69 \\sim C70 \\sim C77: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C61 \\sim C75 \\sim C100 \\sim C97: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C88 \\sim C101 \\sim C98 \\sim N4 \\sim O5: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C9) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(C4) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C85) \\sim Ueq,
Uanis(C60) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C61)
\\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C67) \\sim Ueq,
Uanis(C76) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C69)
\\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C1) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=
 Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=1-FVAR(1)
 Sof(C99)=Sof(H99A)=Sof(H99B)=Sof(H99C)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=
 Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(H85C)=FVAR(1)
 Fixed Sof: C1(0.5) H6A(0.5) H6B(0.5) C5(0.5) H5(0.5) C3(0.5) H3(0.5) C4(0.5)
 H4(0.5) C7(0.5) H7(0.5) C8(0.5) H8(0.5) C9(0.5) H9(0.5) C2(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C01M(H01M), C01O(H01O), C01S(H01S), C01T(H01T), C02R(H02R), C6(H6A), C6(H6B),
 C5(H5), C3(H3), C4(H4), C62(H62), C12(H12), C16(H16), C18(H18), C21(H21),
 C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29), C31(H31),
  C32(H32), C33(H33), C34(H34), C35(H35), C41(H41), C44(H44), C49(H49),
 C54(H54), C57(H57), C78(H78), C81(H81), C94(H94), C95(H95), C7(H7), C8(H8),
 C9(H9), C70(H70), C101(H101)
5.b Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C55(H55A,H55B,H55C), C60(H60A,
 H60B,H60C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C),
 C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C76(H76A,H76B,H76C), C84(H84A,H84B,
 H84C), C61(H61A,H61B,H61C), C97(H97A,H97B,H97C), C75(H75A,H75B,H75C), C90(H90A,
 H90B,H90C), C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C99(H99A,H99B,H99C),
 C87(H87A,H87B,H87C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C73(H73A,H73B,
 H73C), C96(H96A,H96B,H96C), C69(H69A,H69B,H69C), C77(H77A,H77B,H77C), C98(H98A,
 H98B,H98C), C88(H88A,H88B,H88C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 104 electrons were found in a volume of 1588\%A^3^ in 2 voids per unit cell. This is consistent with the presence of 1[C3H7ON] per Formula Unit which account for 80 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              8839
_shelx_fab_checksum              30772
_olex2_submission_special_instructions 'No special instructions were received'