Oligopyrrolic Cu(II)-based tetragonal cage: synthesis, structure, spectral and magnetic properties
Zhu, Zhenhua; Zhao, Chen; Liu, Shuting; Li, Xiao-Lei; Mansikkamäki, Akseli; Tang, Jinkui; Dalton Transactions  (2022) –; doi:10.1039/D2DT02491H

data_7711010
_publ_section_title
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 Oligopyrrolic Cu(II)-based tetragonal cage: synthesis, structure,
 spectral and magnetic properties
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02491H
_journal_year                    2022
_chemical_formula_moiety         'C94 H108 Cu4 N12 O19, 2(C3 H7 N O), 2[C3H7NO]'
_chemical_formula_sum            'C100 H123 Cu4 N14 O21'
_chemical_formula_weight         2110.87
_chemical_name_systematic        Cu4L4
_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             2022-06-27
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_audit_update_record
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2022-06-29 deposited with the CCDC.	2022-08-17 downloaded from the CCDC.
;
_cell_angle_alpha                74.143(2)
_cell_angle_beta                 72.291(2)
_cell_angle_gamma                89.349(2)
_cell_formula_units_Z            1
_cell_length_a                   12.4654(5)
_cell_length_b                   14.3776(6)
_cell_length_c                   16.9641(6)
_cell_measurement_reflns_used    5341
_cell_measurement_temperature    200.15
_cell_measurement_theta_max      24.83
_cell_measurement_theta_min      2.47
_cell_volume                     2777.51(19)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      200.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0856
_diffrn_reflns_av_unetI/netI     0.0700
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            42579
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.041
_diffrn_reflns_theta_max         25.041
_diffrn_reflns_theta_min         2.178
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.825
_exptl_absorpt_correction_T_max  0.921
_exptl_absorpt_correction_T_min  0.906
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_description       block
_exptl_crystal_F_000             1105
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.009
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     704
_refine_ls_number_reflns         9798
_refine_ls_number_restraints     167
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0918
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0431P)^2^+3.2349P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1310
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6545
_reflns_number_total             9798
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02491h2.cif
_cod_data_source_block           2_pl
_cod_database_code               7711010
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.908
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 C48-C46
 1.54 with sigma of 0.01
 C48-C50
 1.54 with sigma of 0.01
 C47-C45
 1.54 with sigma of 0.01
 C47-C49
 1.54 with sigma of 0.01
 Cu1-O10 \\sim Cu1-O10A
 with sigma of 0.02
 C33-C46 \\sim C33-C46A
 with sigma of 0.02
 C16-C45 \\sim C16-C45A
 with sigma of 0.02
 C45-C47 \\sim C45A-C47A
 with sigma of 0.02
 C45-C46 \\sim C45A-C46A
 with sigma of 0.02
 C46-C47 \\sim C46A-C47A
 with sigma of 0.04
 C47-C49 \\sim C47A-C49A
 with sigma of 0.02
 C46-C48 \\sim C46A-C48A
 with sigma of 0.02
 C46-C50 \\sim C46A-C50A
 with sigma of 0.04
 C16-C46 \\sim C16-C46A
 with sigma of 0.04
 C16-C47 \\sim C16-C47A
 with sigma of 0.04
 C33-C45 \\sim C33-C45A
 with sigma of 0.04
 C33-C48 \\sim C33-C48A
 with sigma of 0.04
 C45-C48 \\sim C45A-C48A
 with sigma of 0.04
 C45-C49 \\sim C45A-C49A
 with sigma of 0.04
 C48-C50 \\sim C48A-C50A
 with sigma of 0.02
3. Rigid bond restraints
 C50, C48, C46, C45, C47, C49
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C47 \\sim C45: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C46A \\sim C45A \\sim C47A \\sim C49A \\sim C48A \\sim C50A: within 3.8A with
sigma of 0.02 and sigma for terminal atoms of 0.01 within 3.8A
Uanis(O10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O10A) \\sim Ueq, Uanis(O10A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C48A) \\sim Ueq, Uanis(C50A) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C47A)
\\sim Ueq, Uanis(C49A) \\sim Ueq, Uanis(C49) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: O10(0.15) C45(0.6) C46(0.6) C47(0.6) H47A(0.6) H47B(0.6) C48(0.6)
 H48A(0.6) H48B(0.6) C49(0.6) H49A(0.6) H49B(0.6) H49C(0.6) C50(0.6) H50A(0.6)
 H50B(0.6) H50C(0.6) O10A(0.35) H10A(0.35) H10B(0.35) C46A(0.4) C45A(0.4)
 C49A(0.4) H49D(0.4) H49E(0.4) H49F(0.4) C47A(0.4) H47C(0.4) H47D(0.4)
 C48A(0.4) H48C(0.4) H48D(0.4) C50A(0.4) H50D(0.4) H50E(0.4) H50F(0.4)
6.a Riding coordinates:
 O9(H9), N1(H1), N2(H2), N3(H3), N4(H4)
6.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C24(H24A,H24B), C26(H26A,H26B), C27(H27A,H27B), C29(H29A,
 H29B), C39(H39A,H39B), C47(H47A,H47B), C48(H48A,H48B), O10A(H10A,H10B),
 C47A(H47C,H47D), C48A(H48C,H48D)
6.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C23(H23), C28(H28), C31(H31), C32(H32), C35(H35), C42(H42)
6.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C43(H43A,
 H43B,H43C), C44(H44A,H44B,H44C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C),
 C49A(H49D,H49E,H49F), C50A(H50D,H50E,H50F)
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_smtbx_masks_special_details
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A solvent mask was calculated and 95 electrons were 
found in a volume of 386\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
2[C3H7NO] per Asymmetric Unit 
which account for 80 electrons 
per unit cell.
;
_shelx_res_checksum              68502
_shelx_hkl_checksum              54153
_shelx_fab_checksum              8543
_olex2_submission_special_instructions 'No special instructions were received'