Template-assisted synthesis of isomeric copper(i) clusters with tunable structures showing photophysical and electrochemical properties.
Fang, Jun-Jie; Liu, Zheng; Shen, Yang-Lin; Xie, Yun-Peng; Lu, Xing; Chemical science 14 (2023) 12637–12644; doi:10.1039/d3sc04682f

data_1570111
_publ_section_title
;
 Template-assisted synthesis of isomeric copper(i) clusters with tunable
 structures showing photophysical and electrochemical properties.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              12637
_journal_page_last               12644
_journal_paper_doi               10.1039/d3sc04682f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C180 H288 Cu57 O42 P6 V6, 2(F)'
_chemical_formula_sum            'C180 H288 Cu57 F2 O42 P6 V6'
_chemical_formula_weight         7275.33
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-05-04
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-30 deposited with the CCDC.	2023-10-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.1590(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.0446(6)
_cell_length_b                   19.6458(6)
_cell_length_c                   33.3122(10)
_cell_measurement_reflns_used    9832
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.97
_cell_measurement_theta_min      2.82
_cell_volume                     13064.9(7)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_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      100
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0809
_diffrn_reflns_av_unetI/netI     0.1134
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            99135
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.122
_diffrn_reflns_theta_min         2.274
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.35
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           45.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.817
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.5280
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0892 before and 0.0565 after correction.
The Ratio of minimum to maximum transmission is 0.7082.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear dark black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.849
_exptl_crystal_description       block
_exptl_crystal_F_000             7206
_exptl_crystal_preparation       Solvothemal,Luminescent
_exptl_crystal_recrystallization_method Solvothemal
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.275
_refine_diff_density_min         -1.469
_refine_diff_density_rms         0.151
_refine_ls_extinction_coef       0.00017(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1487
_refine_ls_number_reflns         28771
_refine_ls_number_restraints     1197
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.1686
_refine_ls_R_factor_gt           0.0925
_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^)+(0.0495P)^2^+131.9535P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1752
_refine_ls_wR_factor_ref         0.1984
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15926
_reflns_number_total             28771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04682f2.cif
_cod_data_source_block           fjj2022081210_0m_a
_cod_depositor_comments
'Adding full bibliography for 1570109--1570116.cif.'
_cod_database_code               1570111
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.644
_shelx_estimated_absorpt_t_min   0.596
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C94-C47 = C90-C47 = C96-C47 = C89-C47 = C95-C47 = C84-C47
 1.54 with sigma of 0.02
 C79-C45 = C91-C45 = C80-C45 = C92-C45 = C82-C45 = C93-C45
 1.54 with sigma of 0.02
 Cu24-Cu27 \\sim Cu35-Cu27
 with sigma of 0.02
 Cu24-O17 \\sim Cu35-O17
 with sigma of 0.02
 Cu24-C9 \\sim Cu35-C9
 with sigma of 0.02
 Cu24-Cu28 \\sim Cu35-Cu28
 with sigma of 0.02
 Cu24-C12 \\sim Cu35-C12
 with sigma of 0.02
 C47-C90 \\sim C47-C96
 with sigma of 0.02
 C89-C84 \\sim C90-C84 \\sim C89-C90 \\sim C95-C96 \\sim C95-C94 \\sim C96-C94
 with sigma of 0.02
 Cu24-Cu30 \\sim Cu35-Cu30
 with sigma of 0.02
 Cu24-Cu33 \\sim Cu35-Cu33
 with sigma of 0.02
 C45-C79 \\sim C45-C91
 with sigma of 0.02
 C45-C80 \\sim C45-C92
 with sigma of 0.02
 C45-C82 \\sim C45-C93
 with sigma of 0.02
 C82-C79 \\sim C80-C79 \\sim C82-C80 \\sim C93-C92 \\sim C93-C91 \\sim C91-C92
 with sigma of 0.02
 C47-C84 \\sim C47-C94
 with sigma of 0.02
 C47-C89 \\sim C47-C95
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C65 \\sim C49 \\sim C2 \\sim C81 \\sim C3 \\sim C57 \\sim C4 \\sim C73
\\sim C5 \\sim C89 \\sim C6 \\sim C53 \\sim C7 \\sim C61 \\sim C8 \\sim C69
\\sim C9 \\sim C77 \\sim C10 \\sim C85 \\sim C11 \\sim C93 \\sim C12 \\sim C51
\\sim C13 \\sim C55 \\sim C14 \\sim C59 \\sim C15 \\sim C63 \\sim C16 \\sim C67
\\sim C17 \\sim C71 \\sim C18 \\sim C75 \\sim C19 \\sim C79 \\sim C20 \\sim C83
\\sim C21 \\sim C87 \\sim C22 \\sim C91 \\sim C23 \\sim C95 \\sim C24 \\sim C50
\\sim C25 \\sim C52 \\sim C26 \\sim C54 \\sim C27 \\sim C56 \\sim C28 \\sim C58
\\sim C29 \\sim C60 \\sim C30 \\sim C62 \\sim C31 \\sim C64 \\sim C32 \\sim C66
\\sim C33 \\sim C68 \\sim C34 \\sim C70 \\sim C35 \\sim C72 \\sim C36 \\sim C74
\\sim C37 \\sim C76 \\sim C38 \\sim C78 \\sim C39 \\sim C80 \\sim C40 \\sim C82
\\sim C41 \\sim C84 \\sim C42 \\sim C86 \\sim C43 \\sim C88 \\sim C44 \\sim C90
\\sim C45 \\sim C92 \\sim C46 \\sim C94 \\sim C47 \\sim C96 \\sim C48: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C83 \\sim C36 \\sim C86 \\sim C81 \\sim C27 \\sim C33: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C2 \\sim C8 \\sim C44 \\sim C59 \\sim C66 \\sim C78: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C47 \\sim C84 \\sim C89 \\sim C90 \\sim C94 \\sim C95 \\sim C96 \\sim C9 \\sim
C12: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Cu35 \\sim Cu24: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C45 \\sim C79 \\sim C80 \\sim C82 \\sim C91 \\sim C92 \\sim C93 \\sim C20 \\sim
C14: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C77 \\sim C46 \\sim C62 \\sim C88 \\sim C4 \\sim C17: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C10 \\sim C25 \\sim C51 \\sim C87 \\sim C74 \\sim C85: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C1) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C49) \\sim Ueq, Uanis(C2)
\\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C89)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C7) \\sim Ueq,
Uanis(C61) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C85) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C59) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C71) \\sim Ueq,
Uanis(C18) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C79)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C21) \\sim Ueq,
Uanis(C87) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C50) \\sim Ueq,
Uanis(C25) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C28) \\sim Ueq,
Uanis(C58) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C64) \\sim Ueq,
Uanis(C32) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C68)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(C72) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C78) \\sim Ueq,
Uanis(C39) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C82)
\\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C86) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C92) \\sim Ueq,
Uanis(C46) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C96)
\\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms
of 0.2
Uanis(C27) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C86)
\\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C81) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C66)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C78) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C47) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C90)
\\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C95) \\sim Ueq, Uanis(C96) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(Cu35) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(Cu24) \\sim Ueq, Uanis(Cu35) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C45) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C82)
\\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C93) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C4) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C62)
\\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C77) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C85) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C74)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C10) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Sof(Cu30)=1-FVAR(1)
 Sof(Cu28)=FVAR(1)
 Sof(Cu31)=1-FVAR(2)
 Sof(Cu25)=FVAR(2)
 Sof(Cu33)=1-FVAR(3)
 Sof(Cu27)=FVAR(3)
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=
 Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=1-FVAR(4)
 Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(4)
 Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=
 Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=1-FVAR(5)
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=
 Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=FVAR(5)
 Fixed Sof: Cu24(0.9) Cu26(0.8) Cu29(0.75) Cu32(0.25) Cu34(0.2) Cu35(0.1)
5.a Riding coordinates:
 C59(H59A,H59B,H59C), C96(H96A,H96B,H96C)
5.b Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C37(H37A,H37B,
 H37C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C),
 C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C62(H62A,
 H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C),
 C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,
 H69C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,
 H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C),
 C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,
 H80C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,
 H84B,H84C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C),
 C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C91(H91A,H91B,
 H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,
 H95B,H95C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              54176
_shelx_fab_checksum              19617
_olex2_exptl_crystal_mounting_method MiteGen
_olex2_submission_special_instructions 'No special instructions were received'