Reversible dioxygen uptake at [Cu4] clusters
Osei, Manasseh Kusi; Mirzaei, Saber; Mirzaei, M. Saeed; Valles, Agustin; Hernández Sánchez, Raúl; Chemical Science 15 (2024) 5327–5332; doi:10.1039/D3SC06390A

data_1571175
_publ_section_title
;
 Reversible dioxygen uptake at [Cu4] clusters
;
_journal_issue                   14
_journal_name_full               'Chemical Science'
_journal_page_first              5327
_journal_page_last               5332
_journal_paper_doi               10.1039/D3SC06390A
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety
'C93.51 H115.02 Cu4 N4 O12.378, 0.623(C4 H8 O1), C5 H12'
_chemical_formula_sum            'C101 H132 Cu4 N4 O13'
_chemical_formula_weight         1864.26
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-12
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-13 deposited with the CCDC.	2024-03-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   51.7208(3)
_cell_length_b                   51.7208(3)
_cell_length_c                   23.7243(2)
_cell_measurement_reflns_used    41430
_cell_measurement_temperature    100
_cell_measurement_theta_max      67.9720
_cell_measurement_theta_min      2.6960
_cell_volume                     54961.0(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.961
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -99.00 -53.00   0.50    5.00    --  -54.77 -15.00  60.00   92
  2  \w    -63.00 -23.00   0.50    5.00    --  -54.77 125.00 -30.00   80
  3  \w    -91.00 -18.00   0.50    5.00    --  -54.77   0.00 -30.00  146
  4  \w     26.00  64.00   0.50    5.00    --   63.28 -95.00-180.00   76
  5  \w     25.00  65.00   0.50    5.00    --   63.28 -95.00 -90.00   80
  6  \w     36.00  87.00   0.50    5.00    --   63.28   0.00-120.00  102
  7  \w     49.00  88.00   0.50    5.00    --   63.28-125.00 150.00   78
  8  \w     32.00  63.00   0.50    5.00    --   63.28 -95.00  60.00   62
  9  \w     52.00 101.00   0.50    5.00    --   74.34-125.00-180.00   98
 10  \w     36.00  62.00   0.50    5.00    --   74.34-125.00-150.00   52
 11  \w     45.00  70.00   0.50    5.00    --   74.34 -95.00   0.00   50
 12  \w     56.00 101.00   0.50    5.00    --   74.34-125.00 150.00   90
 13  \w     43.00  98.00   0.50    5.00    --   74.34  15.00  90.00  110
 14  \w     45.00 102.00   0.50    5.00    --   75.91   0.00 -30.00  114
 15  \w     57.00 119.00   0.50    5.00    --   75.91  15.00-180.00  124
 16  \w     37.00 103.00   0.50    5.00    --   75.91-125.00 120.00  132
 17  \w     41.00  66.00   0.50    5.00    --   75.91 -95.00 -30.00   50
 18  \w     66.00  95.00   0.50    5.00    --   78.53-112.00  49.75   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0022543000
_diffrn_orient_matrix_UB_12      0.0054748000
_diffrn_orient_matrix_UB_13      -0.0640881000
_diffrn_orient_matrix_UB_21      0.0061244000
_diffrn_orient_matrix_UB_22      0.0320091000
_diffrn_orient_matrix_UB_23      0.0100908000
_diffrn_orient_matrix_UB_31      0.0337695000
_diffrn_orient_matrix_UB_32      0.0113388000
_diffrn_orient_matrix_UB_33      0.0023944000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       57
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       63
_diffrn_reflns_limit_k_min       -61
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            127669
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.857
_diffrn_reflns_theta_min         2.107
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.169
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86835
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellowish
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_density_diffrn    1.014
_exptl_crystal_description       block
_exptl_crystal_F_000             17748
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         2.452
_refine_diff_density_min         -0.525
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.326
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1120
_refine_ls_number_reflns         23802
_refine_ls_number_restraints     378
_refine_ls_restrained_S_all      1.329
_refine_ls_R_factor_all          0.1243
_refine_ls_R_factor_gt           0.1012
_refine_ls_shift/su_max          1.010
_refine_ls_shift/su_mean         0.016
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3104
_refine_ls_wR_factor_ref         0.3408
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16555
_reflns_number_total             23802
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06390a2.cif
_cod_data_source_block           mo849_rhs1
_cod_depositor_comments
'Adding full bibliography for 1571175--1571176.cif.'
_cod_original_cell_volume        54961.0(8)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1571175
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C N O Cu'
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.902
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C17D, C17E}
{C22D, C22E}
{C23D, C23E}
{C20C, C20G}
3. Restrained distances
 C17C-C18C
 1.5 with sigma of 0.02
 C18C-C19C
 1.5 with sigma of 0.02
 C19C-C20C
 1.5 with sigma of 0.02
 C20C-C21C
 1.5 with sigma of 0.02
 C21C-C22C
 1.5 with sigma of 0.02
 C20C-C22C
 2.5 with sigma of 0.02
 C5SA-C4SA
 1.5 with sigma of 0.02
 C4SA-C3SA
 1.5 with sigma of 0.02
 C3SA-C2SA
 1.5 with sigma of 0.02
 C2SA-C1SA
 1.5 with sigma of 0.02
 C1SA-C3SA
 2.5 with sigma of 0.02
 C2SA-C4SA
 2.5 with sigma of 0.02
 C3SA-C5SA
 2.5 with sigma of 0.02
 C1SB-C2SB
 1.5 with sigma of 0.02
 C2SB-C3SB
 1.5 with sigma of 0.02
 C3SB-C4SB
 1.5 with sigma of 0.02
 C4SB-C5SB
 1.5 with sigma of 0.02
 C1SB-C3SB
 2.5 with sigma of 0.02
 C2SB-C4SB
 2.5 with sigma of 0.02
 C3SB-C5SB
 2.5 with sigma of 0.02
 C22C-C23C
 1.5 with sigma of 0.02
 C21C-C23C
 2.5 with sigma of 0.02
 O1T-C1T
 1.43 with sigma of 0.02
 O1T-C4T
 1.43 with sigma of 0.02
 C4T-C3T
 1.53 with sigma of 0.02
 C3T-C2T
 1.53 with sigma of 0.02
 C2T-C1T
 1.53 with sigma of 0.02
 O1T-C3T
 2.37 with sigma of 0.02
 O1T-C2T
 2.37 with sigma of 0.02
 O1S-C4S
 1.43 with sigma of 0.02
 O1S-C1S
 1.43 with sigma of 0.02
 C1S-C2S
 1.53 with sigma of 0.02
 C2S-C3S
 1.53 with sigma of 0.02
 C3S-C4S
 1.53 with sigma of 0.02
 O1S-C3S
 2.37 with sigma of 0.02
 O1S-C2S
 2.37 with sigma of 0.02
 C4T-C2T
 2.38 with sigma of 0.02
 C3T-C1T
 2.38 with sigma of 0.02
 C1S-C3S
 2.38 with sigma of 0.02
 C2S-C4S
 2.38 with sigma of 0.02
 C20C-C21C = C21C-C22C = C22C-C23C
 1.5 with sigma of 0.02
 C20G-C21G = C21G-C22G = C22G-C23G
 1.5 with sigma of 0.02
 C21G-C23G
 2.5 with sigma of 0.02
 C17E-C18E = C18E-C19E = C19E-C20E = C20E-C21E = C21E-C22E = C22E-C23E = C17D-
 C18D = C18D-C19D = C19D-C20D = C20D-C21D = C21D-C22D = C22D-C23D
 1.5 with sigma of 0.02
4. Rigid bond restraints
 C17D, C23D, C22D, C18D, C19D, C20D, C21D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17E, C18E, C19E, C20E, C21E, C22E, C23E
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C20C, C21C, C22C, C23C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C20G, C21G, C22G, C23G
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17B, C18B, C19B, C20B, C21B, C22B, C23B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C17D \\sim C23D \\sim C22D \\sim C18D \\sim C19D \\sim C20D \\sim C21D: within
2A with sigma of 0.05 and sigma for terminal atoms of 0.1 within 2A
C17E \\sim C18E \\sim C19E \\sim C20E \\sim C21E \\sim C22E \\sim C23E: within
2A with sigma of 0.05 and sigma for terminal atoms of 0.1 within 2A
C20C \\sim C21C \\sim C22C \\sim C23C: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
C20G \\sim C21G \\sim C22G \\sim C23G: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
C17B \\sim C18B \\sim C19B \\sim C20B \\sim C21B \\sim C22B \\sim C23B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C1SA) \\sim Ueq, Uanis(C1SB) \\sim Ueq, Uanis(C2SA) \\sim Ueq,
Uanis(C2SB) \\sim Ueq, Uanis(C3SA) \\sim Ueq, Uanis(C3SB) \\sim Ueq,
Uanis(C4SA) \\sim Ueq, Uanis(C4SB) \\sim Ueq, Uanis(C5SA) \\sim Ueq,
Uanis(C5SB) \\sim Ueq: with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(O1T) \\sim Ueq, Uanis(O1S) \\sim Ueq, Uanis(C1T) \\sim Ueq, Uanis(C1S)
\\sim Ueq, Uanis(C4T) \\sim Ueq, Uanis(C4S) \\sim Ueq, Uanis(C2T) \\sim Ueq,
Uanis(C2S) \\sim Ueq, Uanis(C3T) \\sim Ueq, Uanis(C3S) \\sim Ueq: with sigma of
0.03 and sigma for terminal atoms of 0.06
Uanis(C7C) \\sim Ueq, Uanis(N1D) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C1SA) = Uanis(C1SB) = Uanis(C2SA) = Uanis(C2SB) = Uanis(C3SA) =
Uanis(C3SB) = Uanis(C4SA) = Uanis(C4SB) = Uanis(C5SA) = Uanis(C5SB)
Uanis(O1T) = Uanis(O1S) = Uanis(C1T) = Uanis(C1S) = Uanis(C4T) = Uanis(C4S) =
Uanis(C2T) = Uanis(C2S) = Uanis(C3T) = Uanis(C3S)
Uanis(C17D) = Uanis(C17E)
Uanis(C18D) = Uanis(C18E)
Uanis(C19D) = Uanis(C19E)
Uanis(C20D) = Uanis(C20E)
Uanis(C21D) = Uanis(C21E)
Uanis(C22D) = Uanis(C22E)
Uanis(C23D) = Uanis(C23E)
Uanis(C20C) = Uanis(C20G)
Uanis(C21C) = Uanis(C21G)
Uanis(C22C) = Uanis(C22G)
Uanis(C23C) = Uanis(C23G)
6. Others
 Sof(C1SB)=Sof(H1SD)=Sof(H1SE)=Sof(H1SF)=Sof(C2SB)=Sof(H2SC)=Sof(H2SD)=
 Sof(C3SB)=Sof(H3SC)=Sof(H3SD)=Sof(C4SB)=Sof(H4SC)=Sof(H4SD)=Sof(C5SB)=
 Sof(H5SD)=Sof(H5SE)=Sof(H5SF)=1-FVAR(1)
 Sof(C1SA)=Sof(H1SA)=Sof(H1SB)=Sof(H1SC)=Sof(C2SA)=Sof(H2SA)=Sof(H2SB)=
 Sof(C3SA)=Sof(H3SA)=Sof(H3SB)=Sof(C4SA)=Sof(H4SA)=Sof(H4SB)=Sof(C5SA)=
 Sof(H5SA)=Sof(H5SB)=Sof(H5SC)=FVAR(1)
 Sof(O1S)=Sof(C1S)=Sof(H1SG)=Sof(H1SH)=Sof(C2S)=Sof(H2SE)=Sof(H2SF)=Sof(C3S)=
 Sof(H3SE)=Sof(H3SF)=Sof(C4S)=Sof(H4SE)=Sof(H4SF)=1-FVAR(2)
 Sof(O1T)=Sof(C1T)=Sof(H1TA)=Sof(H1TB)=Sof(C2T)=Sof(H2TA)=Sof(H2TB)=Sof(C3T)=
 Sof(H3TA)=Sof(H3TB)=Sof(C4T)=Sof(H4TA)=Sof(H4TB)=FVAR(2)
 Sof(C22E)=Sof(H22A)=Sof(H22B)=Sof(C17E)=Sof(H17C)=Sof(H17D)=Sof(C23E)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(H16E)=Sof(C18E)=Sof(H18I)=Sof(H18J)=
 Sof(C19E)=Sof(H19K)=Sof(H19L)=Sof(C20E)=Sof(H20K)=Sof(H20L)=Sof(C21E)=
 Sof(H21I)=Sof(H21J)=1-FVAR(3)
 Sof(C17D)=Sof(H17A)=Sof(H17B)=Sof(C23D)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C22D)=Sof(H22C)=Sof(H22D)=Sof(H16D)=Sof(C18D)=Sof(H18G)=Sof(H18H)=
 Sof(C19D)=Sof(H19I)=Sof(H19J)=Sof(C20D)=Sof(H20I)=Sof(H20J)=Sof(C21D)=
 Sof(H21G)=Sof(H21H)=FVAR(3)
 Sof(C20G)=Sof(H20C)=Sof(H20D)=Sof(H19G)=Sof(H19H)=Sof(C21G)=Sof(H21K)=
 Sof(H21L)=Sof(C22G)=Sof(H22K)=Sof(H22L)=Sof(C23G)=Sof(H23P)=Sof(H23Q)=
 Sof(H23R)=1-FVAR(4)
 Sof(C20C)=Sof(H20A)=Sof(H20B)=Sof(H19E)=Sof(H19F)=Sof(C21C)=Sof(H21E)=
 Sof(H21F)=Sof(C22C)=Sof(H22I)=Sof(H22J)=Sof(C23C)=Sof(H23M)=Sof(H23N)=
 Sof(H23O)=FVAR(4)
7.a Ternary CH refined with riding coordinates:
 N1A(H1A), N1B(H1B), N1C(H1C), N1D(H1D), C16A(H16A), C16B(H16B), C16C(H16C),
 C16D(H16D), C16D(H16E)
7.b Secondary CH2 refined with riding coordinates:
 C22E(H22A,H22B), C20C(H20A,H20B), C17D(H17A,H17B), C22D(H22C,H22D), C17E(H17C,
 H17D), C8A(H8AA,H8AB), C8B(H8BA,H8BB), C8C(H8CA,H8CB), C8D(H8DA,H8DB),
 C20G(H20C,H20D), C15A(H15A,H15B), C15B(H15C,H15D), C15C(H15E,H15F), C15D(H15G,
 H15H), C17A(H17E,H17F), C17B(H17G,H17H), C17C(H17I,H17J), C18A(H18A,H18B),
 C18B(H18C,H18D), C18C(H18E,H18F), C18D(H18G,H18H), C18E(H18I,H18J), C19A(H19A,
 H19B), C19B(H19C,H19D), C19C(H19E,H19F), C19C(H19G,H19H), C19D(H19I,H19J),
 C19E(H19K,H19L), C20A(H20E,H20F), C20B(H20G,H20H), C20D(H20I,H20J), C20E(H20K,
 H20L), C21A(H21A,H21B), C21B(H21C,H21D), C21C(H21E,H21F), C21D(H21G,H21H),
 C21E(H21I,H21J), C21G(H21K,H21L), C22A(H22E,H22F), C22B(H22G,H22H), C22C(H22I,
 H22J), C22G(H22K,H22L), C1S(H1SG,H1SH), C2S(H2SE,H2SF), C3S(H3SE,H3SF),
 C4S(H4SE,H4SF), C1T(H1TA,H1TB), C2T(H2TA,H2TB), C3T(H3TA,H3TB), C4T(H4TA,H4TB),
  C2SA(H2SA,H2SB), C2SB(H2SC,H2SD), C3SA(H3SA,H3SB), C3SB(H3SC,H3SD), C4SA(H4SA,
 H4SB), C4SB(H4SC,H4SD)
7.c Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C2B(H2B), C2C(H2C), C2D(H2D), C4A(H4A), C4B(H4B), C4C(H4C),
 C4D(H4D), C5A(H5A), C5B(H5B), C5C(H5C), C5D(H5D), C12A(H12A), C12B(H12B),
 C12C(H12C), C12D(H12D)
7.d Idealised Me refined as rotating group:
 C23D(H23A,H23B,H23C), C7A(H7AA,H7AB,H7AC), C7B(H7BA,H7BB,H7BC), C7C(H7CA,H7CB,
 H7CC), C7D(H7DA,H7DB,H7DC), C23E(H23D,H23E,H23F), C23A(H23G,H23H,H23I),
 C23B(H23J,H23K,H23L), C23C(H23M,H23N,H23O), C23G(H23P,H23Q,H23R), C1SA(H1SA,
 H1SB,H1SC), C1SB(H1SD,H1SE,H1SF), C5SA(H5SA,H5SB,H5SC), C5SB(H5SD,H5SE,H5SF)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              30897
_shelx_fab_checksum              50901
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.820
_oxdiff_exptl_absorpt_empirical_full_min 0.736