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_7712764
_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
'C102 H105 Cl2 Cu8 O21 P3 S8, 2(C3 H7 N O), 5[C3H7ON]'
_chemical_formula_sum            'C108 H119 Cl2 Cu8 N2 O23 P3 S8'
_chemical_formula_weight         2741.65
_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
_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                74.314(2)
_cell_angle_beta                 68.612(2)
_cell_angle_gamma                75.244(2)
_cell_formula_units_Z            2
_cell_length_a                   17.1459(11)
_cell_length_b                   20.4847(15)
_cell_length_c                   22.6894(14)
_cell_measurement_reflns_used    9946
_cell_measurement_temperature    150
_cell_measurement_theta_max      50.14
_cell_measurement_theta_min      2.56
_cell_volume                     7034.8(8)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_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  0.1030
_diffrn_reflns_av_unetI/netI     0.1168
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            79283
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        51.433
_diffrn_reflns_theta_max         51.433
_diffrn_reflns_theta_min         2.557
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           2.86
_diffrn_source_power             0.1997996
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.896
_exptl_absorpt_correction_T_max  0.7501
_exptl_absorpt_correction_T_min  0.5860
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1472 before and 0.0701 after correction.
The Ratio of minimum to maximum transmission is 0.7812.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear blackish black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       cube
_exptl_crystal_F_000             2808
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         1.732
_refine_diff_density_min         -0.826
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1533
_refine_ls_number_reflns         23140
_refine_ls_number_restraints     558
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.1350
_refine_ls_R_factor_gt           0.0781
_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^)+(0.1348P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2132
_refine_ls_wR_factor_ref         0.2457
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12326
_reflns_number_total             23140
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00455d2.cif
_cod_data_source_block           Cu16L4-Sa
_cod_original_cell_volume        7034.9(8)
_cod_database_code               7712764
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.200
_shelx_estimated_absorpt_t_min   0.110
_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
 C68-C100
 1.4 with sigma of 0.01
 C100-C91
 1.4 with sigma of 0.01
 C7-O1
 1.55 with sigma of 0.01
 C62-C82
 2.55 with sigma of 0.01
 C02U-C2 \\sim C02U-C4
 with sigma of 0.02
 C02U-C5 \\sim C02U-C6
 with sigma of 0.02
 C02U-C8 \\sim C02U-C1
 with sigma of 0.02
 C102-C109 \\sim C102-C87
 with sigma of 0.02
 C102-C3 \\sim C102-C110
 with sigma of 0.02
 C102-C84 \\sim C102-C111
 with sigma of 0.02
3. Rigid bond restraints
 C68, C100
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C91, C100
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
O7 \\sim C61 \\sim C68 \\sim C100 \\sim C91 \\sim O6 \\sim O2 \\sim O8: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O7 \\sim C61: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C71 \\sim C66 \\sim C86 \\sim C72 \\sim C83 \\sim C33: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C64 \\sim C94 \\sim C90 \\sim C46 \\sim C93 \\sim C67: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C95 \\sim C62 \\sim C63 \\sim C65 \\sim C81 \\sim C82: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C98 \\sim C69 \\sim C97 \\sim C96: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C3 \\sim C102 \\sim C84 \\sim C109: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C80 \\sim C79 \\sim C19 \\sim C99: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C7 \\sim N104 \\sim C103 \\sim C85: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C89 \\sim C88 \\sim N92 \\sim C101 \\sim O5: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C109 \\sim C87 \\sim C3 \\sim C110 \\sim C84 \\sim C111: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1 \\sim C2 \\sim C4 \\sim C5 \\sim C6 \\sim C8: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(C91) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C100)
\\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C98) \\sim Ueq,
Uanis(C95) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C35)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C66) \\sim Ueq,
Uanis(C83) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C93)
\\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C82) \\sim Ueq,
Uanis(C81) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C71)
\\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C72) \\sim Ueq,
Uanis(C30) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C3)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(N104) \\sim Ueq, Uanis(C103) \\sim Ueq,
Uanis(C85) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C87)
\\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C109) \\sim Ueq,
Uanis(C3) \\sim Ueq, Uanis(C84) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5. Others
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C82)=Sof(H82A)=Sof(H70)=Sof(H82B)=
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=1-FVAR(1)
 Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=
 Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=FVAR(1)
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(2)
 Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(H4C)=1-FVAR(3)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(3)
 Sof(C110)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C111)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=Sof(C87)=Sof(H87A)=Sof(H87B)=Sof(H87C)=1-FVAR(4)
 Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=
 Sof(C109)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(4)
6.a Riding coordinates:
 C66(H66A,H66B,H66C), C82(H82A,H70,H82B), C72(H72A,H72B,H72C), C110(H11A,H11B,
 H11C), C111(H11D,H11E,H11F), C87(H87A,H87B,H87C)
6.b Secondary CH2 refined with riding coordinates:
 C67(H67A,H67B), C93(H93A,H93B)
6.c Aromatic/amide H refined with riding coordinates:
 C49(H49), C47(H47), C74(H74), C12(H12), C14(H14), C56(H56), C20(H20),
 C60(H60), C24(H24), C26(H26), C76(H76), C02E(H02E), C51(H51), C18(H18), C9(H9),
  C108(H108), C43(H43), C94(H94), C53(H53), C42(H42), C40(H40), C32(H32),
 C36(H36), C38(H38), C64(H64), C34(H34), C41(H41), C35(H35), C46(H46), C7(H7),
 C101(H101)
6.d Idealised Me refined as rotating group:
 C79(H79A,H79B,H79C), C03B(H03A,H03B,H03C), C3(H3A,H3B,H3C), C48(H48A,H48B,
 H48C), C98(H98A,H98B,H98C), C84(H84A,H84B,H84C), C31(H31A,H31B,H31C), C99(H99A,
 H99B,H99C), C30(H30A,H30B,H30C), C03N(H03D,H03E,H03F), C19(H19A,H19B,H19C),
 C69(H69A,H69B,H69C), C29(H29A,H29B,H29C), C83(H83A,H83B,H83C), C109(H10A,H10B,
 H10C), C97(H97A,H97B,H97C), C95(H95A,H95B,H95C), C81(H81A,H81B,H81C), C71(H71A,
 H71B,H71C), C63(H63A,H63B,H63C), C62(H62A,H62B,H62C), C65(H65A,H65B,H65C),
 C86(H86A,H86B,H86C), C33(H33A,H33B,H33C), C85(H85A,H85B,H85C), C103(H10D,H10E,
 H10F), C89(H89A,H89B,H89C), C88(H88A,H88B,H88C), C2(H2A,H2B,H2C), C5(H5A,H5B,
 H5C), C8(H8A,H8B,H8C), C6(H6A,H6B,H6C), C1(H1A,H1B,H1C), C4(H4A,H4B,H4C)
;
_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              88608
_shelx_fab_checksum              93142
_olex2_submission_special_instructions 'No special instructions were received'