Supramolecular assemblies of Cu(II) with a tetraphenylethene-imidazole ligand for tuning photocatalytic CO<sub>2</sub> reduction.
Qiu, Zhao-Feng; Wang, Peng; Zhang, Xiao-Yu; Chen, Jia-Qi; Zhang, Kai-Yang; Lu, Xiang-Yu; Zhao, Yue; Sun, Wei-Yin; Chemical communications (Cambridge, England) 60 (2024) 2204–2207; doi:10.1039/d3cc05514k

data_7132787
_publ_section_title
;
 Supramolecular assemblies of Cu(II) with a tetraphenylethene-imidazole
 ligand for tuning photocatalytic CO<sub>2</sub> reduction.
;
_journal_issue                   16
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2204
_journal_page_last               2207
_journal_paper_doi               10.1039/d3cc05514k
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C76 H60 Cu2 N16 O2, 4(N O3), 2.5(H2 O)'
_chemical_formula_sum            'C76 H65 Cu2 N20 O16.5'
_chemical_formula_weight         1649.56
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-10-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-11-08 deposited with the CCDC.	2024-01-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.7601(8)
_cell_length_b                   19.7601(8)
_cell_length_c                   19.9303(11)
_cell_measurement_reflns_used    9940
_cell_measurement_temperature    190.00
_cell_measurement_theta_max      48.46
_cell_measurement_theta_min      2.74
_cell_volume                     7782.0(6)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      190.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0527
_diffrn_reflns_av_unetI/netI     0.0660
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            60540
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.036
_diffrn_reflns_theta_min         1.945
_diffrn_source_current           2.86
_diffrn_source_power             0.1993706
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.387
_exptl_absorpt_correction_T_max  0.1422
_exptl_absorpt_correction_T_min  0.0645
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1197 before and 0.0915 after correction.
The Ratio of minimum to maximum transmission is 0.4536.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.408
_exptl_crystal_description       block
_exptl_crystal_F_000             3404
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.335
_refine_diff_density_min         -0.424
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.091(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1421
_refine_ls_number_reflns         13904
_refine_ls_number_restraints     794
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0976
_refine_ls_R_factor_gt           0.0786
_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^)+(0.0637P)^2^+23.8508P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1978
_refine_ls_wR_factor_ref         0.2061
_reflns_Friedel_coverage         0.887
_reflns_Friedel_fraction_full    0.948
_reflns_Friedel_fraction_max     0.941
_reflns_number_gt                10709
_reflns_number_total             13904
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc05514k2.cif
_cod_data_source_block           Cu-H2O
_cod_original_cell_volume        7782.0(8)
_cod_original_formula_sum        'C76 H65 Cu2 N20 O16.50'
_cod_database_code               7132787
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.707
_shelx_estimated_absorpt_t_min   0.649
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.909(9)
 0.091(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
3. Restrained distances
 N17-O4 = N17-O5
 1.25 with sigma of 0.02
 N17-O6
 1.24 with sigma of 0.02
 N17A-O6A = N17A-O4A
 1.25 with sigma of 0.02
 N17A-O5A
 1.24 with sigma of 0.02
 N18-O8 = N18-O9
 1.25 with sigma of 0.02
 N18-O7
 1.24 with sigma of 0.02
 N18A-O9A = N18A-O7A
 1.25 with sigma of 0.02
 N18A-O8A
 1.24 with sigma of 0.02
 N20-O14 = N20-O13
 1.25 with sigma of 0.02
 N20-O15
 1.24 with sigma of 0.02
 N19A-O12A = N19A-O10A
 1.25 with sigma of 0.02
 N19A-O11A
 1.24 with sigma of 0.02
 N20A-O14A = N20A-O13A
 1.25 with sigma of 0.02
 N20A-O15A
 1.24 with sigma of 0.02
 N19-O12 = N19-O10
 1.25 with sigma of 0.02
 N19-O11
 1.24 with sigma of 0.02
 C52A-C51A \\sim C52-C51 \\sim C53-C52A \\sim C53-C52 \\sim C51-C50 \\sim
C51A-C50 \\sim C55-C54 ~
 C55A-C54A \\sim C55A-C50 \\sim C55-C50 \\sim C54-C53 \\sim C54A-C53
 with sigma of 0.02
 C33-C32 \\sim C33-C32A \\sim C32A-C31A \\sim C32-C31 \\sim C31A-C30 \\sim
C31-C30 \\sim C35A-C30 ~
 C35-C30 \\sim C35-C34 \\sim C35A-C34A \\sim C34A-C33 \\sim C34-C33
 with sigma of 0.02
 C70-C69 \\sim C70A-C69A \\sim C71-C70A \\sim C71-C70 \\sim C69A-C68 \\sim
C69-C68
 with sigma of 0.02
 C26-C25 \\sim C26A-C25A \\sim C26-C21 \\sim C26A-C21 \\sim C25-C24 \\sim
C25A-C24 \\sim C24-C23A ~
 C24-C23 \\sim C23-C22 \\sim C24A-C23A \\sim C24A-C21 \\sim C22-C21
 with sigma of 0.02
 O4-O6 \\sim O6-O5 \\sim O5-O4
 with sigma of 0.04
 O6A-O5A \\sim O5A-O4A \\sim O4A-O6A
 with sigma of 0.04
 O8-O7 \\sim O7-O9 \\sim O9-O8
 with sigma of 0.04
 O9A-O8A \\sim O8A-O7A \\sim O7A-O9A
 with sigma of 0.04
 O14-O15 \\sim O15-O13 \\sim O13-O14
 with sigma of 0.04
 O12A-O11A \\sim O11A-O10A \\sim O10A-O12A
 with sigma of 0.04
 O14A-O15A \\sim O15A-O13A \\sim O13A-O14A
 with sigma of 0.04
 O12-O11 \\sim O11-O10 \\sim O10-O12
 with sigma of 0.04
4. Restrained planarity
 C68, C70, C71, C72, C73
 with sigma of 0.1
 O4, O5, O6, N17
 with sigma of 0.1
 O4A, O5A, O6A, N17A
 with sigma of 0.1
 O7, O8, O9, N18
 with sigma of 0.1
 O7A, O8A, O9A, N18A
 with sigma of 0.1
 O13, O14, O15, N20
 with sigma of 0.1
 O10A, O11A, O12A, N19A
 with sigma of 0.1
 O13A, O14A, O15A, N20A
 with sigma of 0.1
 O10, O11, O12, N19
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C23A \\sim C24A \\sim C25 \\sim C25A \\sim C26 \\sim C26A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C60A \\sim C61A \\sim C63A \\sim C64A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C12 \\sim C12A \\sim C13 \\sim C13A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O4 \\sim O5 \\sim O6 \\sim N17: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O4A \\sim O5A \\sim O6A \\sim N17A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O7 \\sim O8 \\sim O9 \\sim N18: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O7A \\sim O8A \\sim O9A \\sim N18A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O13 \\sim O14 \\sim O15 \\sim N20: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O10A \\sim O11A \\sim O12A \\sim N19A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O13A \\sim O14A \\sim O15A \\sim N20A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O10 \\sim O11 \\sim O12 \\sim N19: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C63 \\sim C63A \\sim C64 \\sim C64A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C31) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C32)
\\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C32A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C51A) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C54A)
\\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C55A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C70A) \\sim Ueq, Uanis(C69A) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C69)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C34A) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C35A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 C25, C26A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O4, O5, O6, N17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O4A, O5A, O6A, N17A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O7, O8, O9, N18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O7A, O8A, O9A, N18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, O14, O15, N20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O10A, O11A, O12A, N19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13A, O14A, O15A, N20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O10, O11, O12, N19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(H16A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=
 Sof(C26A)=Sof(H26A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C34A)=
 Sof(H34A)=Sof(C35A)=Sof(H35A)=Sof(C51A)=Sof(H51A)=Sof(C52A)=Sof(H52A)=
 Sof(C54A)=Sof(H54A)=Sof(C55A)=Sof(H55A)=Sof(C60A)=Sof(H60A)=Sof(C61A)=
 Sof(H61A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=Sof(H64A)=Sof(C69A)=Sof(H69A)=
 Sof(C70A)=Sof(H70A)=Sof(C72A)=Sof(H72A)=Sof(C73A)=Sof(H73A)=Sof(O7A)=Sof(O8A)=
 Sof(O9A)=Sof(N18A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=Sof(N19A)=Sof(O4A)=Sof(O5A)=
 Sof(O6A)=Sof(N17A)=Sof(O13A)=Sof(O14A)=Sof(O15A)=Sof(N20A)=Sof(O16A)=Sof(H16B)=
 Sof(H16C)=Sof(O17A)=Sof(H17C)=Sof(H17D)=1-FVAR(1)
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=
 Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=
 Sof(C51)=Sof(H51)=Sof(C52)=Sof(H52)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55)=
 Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61)=Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=
 Sof(C69)=Sof(H69)=Sof(C70)=Sof(H70)=Sof(C72)=Sof(H72)=Sof(C73)=Sof(H73)=
 Sof(O13)=Sof(O14)=Sof(O15)=Sof(N20)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(N17)=Sof(O7)=
 Sof(O8)=Sof(O9)=Sof(N18)=Sof(O10)=Sof(O11)=Sof(O12)=Sof(N19)=Sof(O17)=
 Sof(H17A)=Sof(H17B)=Sof(O16)=Sof(H16D)=Sof(H16E)=FVAR(1)
 Fixed Sof: O3(0.5) H3A(0.5) H3B(0.5)
8.a Everything fixed:
 H3A, H3B, H16B, H16C, H17A, H17B, H17C, H17D
8.b Free rotating group:
 O16(H16D,H16E)
8.c Rotating group:
 O1(H1A,H1B), O2(H2A,H2B)
8.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C12(H12), C12A(H12A),
 C13(H13), C13A(H13A), C15(H15), C15A(H15A), C16(H16), C16A(H16A), C17(H17),
 C18(H18), C19(H19), C22(H22), C23(H23), C23A(H23A), C24A(H24A), C25(H25),
 C25A(H25A), C26(H26), C26A(H26A), C27(H27), C28(H28), C29(H29), C31(H31),
 C31A(H31A), C32(H32), C32A(H32A), C34(H34), C34A(H34A), C35(H35), C35A(H35A),
 C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C43(H43), C44(H44),
  C46(H46), C47(H47), C51(H51), C51A(H51A), C52(H52), C52A(H52A), C54(H54),
 C54A(H54A), C55(H55), C55A(H55A), C56(H56), C57(H57), C58(H58), C60(H60),
 C60A(H60A), C61(H61), C61A(H61A), C63(H63), C63A(H63A), C64(H64), C64A(H64A),
 C65(H65), C66(H66), C67(H67), C69(H69), C69A(H69A), C70(H70), C70A(H70A),
 C72(H72), C72A(H72A), C73(H73), C73A(H73A), C74(H74), C75(H75), C76(H76)
;
_shelx_res_checksum              88641
_shelx_hkl_checksum              88810
_olex2_submission_special_instructions 'No special instructions were received'