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_1571176
_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         'C91 H110 Cu4 N4 O12, C2 H3 N, 0.25(C4 H8 O)'
_chemical_formula_sum            'C94 H115 Cu4 N5 O12.25'
_chemical_formula_weight         1765.06
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-20 deposited with the CCDC.	2024-03-05 downloaded from the CCDC.
;
_cell_angle_alpha                107.861(2)
_cell_angle_beta                 104.915(2)
_cell_angle_gamma                94.308(2)
_cell_formula_units_Z            2
_cell_length_a                   14.3434(3)
_cell_length_b                   18.4638(5)
_cell_length_c                   19.1152(5)
_cell_measurement_reflns_used    18535
_cell_measurement_temperature    100
_cell_measurement_theta_max      73.2020
_cell_measurement_theta_min      2.5180
_cell_volume                     4590.2(2)
_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 0.994
_diffrn_measured_fraction_theta_max 0.957
_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     37.00  69.00   0.50    3.00    --   34.00  77.00  22.66   64
  2  \w     37.00  69.00   0.50    3.00    --   34.00  77.00  89.16   64
  3  \w    -74.00 -42.00   0.50    3.00    --  -38.00 -75.00 -58.37   64
  4  \w     47.00  79.00   0.50    3.00    --   38.00  64.00-118.95   64
  5  \w    -74.00 -42.00   0.50    3.00    --  -38.00 -75.00 -16.42   64
  6  \w     56.00  88.00   0.50    3.00    --   46.00  60.00 -87.78   64
  7  \w    -85.00 -54.00   0.50    3.00    --  -46.00 -67.00  18.02   62
  8  \w    -91.00 -60.00   0.50    3.00    --  -54.00 -72.00 130.70   62
  9  \w    -81.00 -13.00   0.50    3.00    --  -54.77 125.00 120.00  136
 10  \w    -81.00 -13.00   0.50    3.00    --  -54.77 125.00 120.00  136
 11  \w   -105.00 -68.00   0.50    3.00    --  -58.00 -36.00  -6.74   74
 12  \w   -105.00 -68.00   0.50    3.00    --  -58.00 -36.00  38.65   74
 13  \w   -105.00 -68.00   0.50    3.00    --  -58.00 -36.00  77.70   74
 14  \w   -109.00 -73.00   0.50    3.00    --  -62.00 -37.00-160.41   72
 15  \w   -106.00 -73.00   0.50    3.00    --  -62.25 -53.00 165.52   66
 16  \w   -109.00 -75.00   0.50    3.00    --  -62.25 -39.00  61.97   68
 17  \w   -109.00 -75.00   0.50    3.00    --  -62.25 -39.00 -68.11   68
 18  \w   -105.00 -72.00   0.50    3.00    --  -62.25 -56.00 179.35   66
 19  \w   -108.00 -74.00   0.50    3.00    --  -62.25 -42.00  98.36   68
 20  \w   -109.00 -72.00   0.50    3.00    --  -62.25 -36.00 -42.36   74
 21  \w     34.00  90.00   0.50    3.00    --   63.28-125.00 -30.00  112
 22  \w     34.00  90.00   0.50    3.00    --   63.28-125.00 -60.00  112
 23  \w     34.00  90.00   0.50    3.00    --   63.28-125.00 120.00  112
 24  \w     70.00 102.00   0.50    3.00    --   66.00  76.00 -87.25   64
 25  \w     37.00  83.00   0.50    3.00    --   74.34 -95.00 -30.00   92
 26  \w     37.00  83.00   0.50    3.00    --   74.34 -95.00  90.00   92
 27  \w     37.00  83.00   0.50    3.00    --   74.34 -95.00 120.00   92
 28  \w     37.00  83.00   0.50    3.00    --   74.34 -95.00 -90.00   92
 29  \w     34.00 101.00   0.50    3.00    --   74.34-125.00-180.00  134
 30  \w     34.00 101.00   0.50    3.00    --   74.34-125.00  30.00  134
 31  \w     43.00 120.00   0.50    3.00    --   74.34  15.00 150.00  154
 32  \w     34.00  92.00   0.50    3.00    --   74.34-110.00 -90.00  116
 33  \w     34.00 101.00   0.50    3.00    --   74.34-125.00  30.00  134
 34  \w     37.00  83.00   0.50    3.00    --   74.34 -95.00-180.00   92
 35  \w     37.00  83.00   0.50    3.00    --   74.34 -95.00 150.00   92
 36  \w     37.00  83.00   0.50    3.00    --   74.34 -95.00   0.00   92
 37  \w     47.00  83.00   0.50    3.00    --   74.34 -95.00  60.00   72
 38  \w     76.00 102.00   0.50    3.00    --   75.91-125.00-180.00   52
 39  \w     77.00 103.00   0.50    3.00    --   75.91-125.00  90.00   52
 40  \w     46.00 102.00   0.50    3.00    --   75.91   0.00-120.00  112
 41  \w     74.00 103.00   0.50    3.00    --   75.91-125.00 -30.00   58
 42  \w     34.00  70.00   0.50    3.00    --   75.91-125.00 -30.00   72
 43  \w     40.00 103.00   0.50    3.00    --   75.91   0.00 -60.00  126
 44  \w     77.00 103.00   0.50    3.00    --   75.91-125.00 -60.00   52
 45  \w     74.00 100.00   0.50    3.00    --   78.53-116.00-131.99   52
 46  \w     72.00  98.00   0.50    3.00    --   78.53-113.00 126.03   52
 47  \w     39.00 104.00   0.50    3.00    --   78.53-122.00  61.97  130
 48  \w     93.00 126.00   0.50    3.00    --   78.53  35.00 155.42   66
 49  \w     75.00 101.00   0.50    3.00    --   78.53-119.00-148.19   52
 50  \w     93.00 124.00   0.50    3.00    --   78.53  45.00 -45.96   62
 51  \w     84.00 125.00   0.50    3.00    --   78.53  27.00 -68.45   82
 52  \w     94.00 121.00   0.50    3.00    --   78.53  35.00  58.81   54
 53  \w     38.00  68.00   0.50    3.00    --   78.53-119.00-148.19   60
 54  \w     38.00 100.00   0.50    3.00    --   78.53-117.00-109.97  124
 55  \w     81.00 107.00   0.50    3.00    --   78.53-126.00  34.72   52
;
_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      -0.0316338000
_diffrn_orient_matrix_UB_12      -0.0800572000
_diffrn_orient_matrix_UB_13      -0.0632550000
_diffrn_orient_matrix_UB_21      0.0469316000
_diffrn_orient_matrix_UB_22      -0.0375542000
_diffrn_orient_matrix_UB_23      0.0591898000
_diffrn_orient_matrix_UB_31      -0.0975078000
_diffrn_orient_matrix_UB_32      -0.0093232000
_diffrn_orient_matrix_UB_33      0.0187314000
_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  0.0633
_diffrn_reflns_av_unetI/netI     0.0754
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            89646
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.470
_diffrn_reflns_theta_min         2.542
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.525
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80488
_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    1.277
_exptl_crystal_description       block
_exptl_crystal_F_000             1856
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.883
_refine_diff_density_min         -0.585
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1090
_refine_ls_number_reflns         17927
_refine_ls_number_restraints     241
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.1907
_refine_ls_R_factor_gt           0.1052
_refine_ls_shift/su_max          5.487
_refine_ls_shift/su_mean         0.055
_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          0.2911
_refine_ls_wR_factor_ref         0.3509
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8476
_reflns_number_total             17927
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06390a2.cif
_cod_data_source_block           mo860_rhs1
_cod_depositor_comments
'Adding full bibliography for 1571175--1571176.cif.'
_cod_database_code               1571176
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C N O Cu'
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.901
_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
{C19A, C19E}
{C22A, C22E}
{C23A, C23E}
{C19B, C19F}
{C17D, C17G}
3. Restrained distances
 C18A-C19A = C19A-C20A = C20A-C21A = C21A-C22A = C22A-C23A = C18A-C19E = C19E-
 C20E = C20E-C21E = C21E-C22E = C22E-C23E
 1.5 with sigma of 0.02
 C18B-C19B = C19B-C20B = C20B-C21B = C21B-C22B = C18B-C19F = C19F-C20F = C20F-
 C21F = C21F-C22F
 1.5 with sigma of 0.02
 C19F-C21F = C20F-C22F
 2.5 with sigma of 0.02
 C19B-C21B = C20B-C22B
 2.5 with sigma of 0.02
 C17D-C18D
 1.5 with sigma of 0.02
 C18D-C19D
 1.5 with sigma of 0.02
 C19D-C20D
 1.5 with sigma of 0.02
 C20D-C21D
 1.5 with sigma of 0.02
 C21D-C22D
 1.5 with sigma of 0.02
 C22D-C23D
 1.5 with sigma of 0.02
 C17G-C18G
 1.5 with sigma of 0.02
 C18G-C19G
 1.5 with sigma of 0.02
 C19G-C20G
 1.5 with sigma of 0.02
 C20G-C21G
 1.5 with sigma of 0.02
 C21G-C22G
 1.5 with sigma of 0.02
 C22G-C23G
 1.5 with sigma of 0.02
 C17D-C19D
 2.5 with sigma of 0.02
 C18D-C20D
 2.5 with sigma of 0.02
 C19D-C21D
 2.5 with sigma of 0.02
 C20D-C22D
 2.5 with sigma of 0.02
 C21D-C23D
 2.5 with sigma of 0.02
 C17G-C19G
 2.5 with sigma of 0.02
 C18G-C20G
 2.5 with sigma of 0.02
 C19G-C21G
 2.5 with sigma of 0.02
 C20G-C22G
 2.5 with sigma of 0.02
 C21G-C23G
 2.5 with sigma of 0.02
 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
 C22C-C23C
 1.5 with sigma of 0.02
 O1S-C11S
 1.43 with sigma of 0.02
 O1S-C14S
 1.43 with sigma of 0.02
 C11S-C12S
 1.54 with sigma of 0.02
 C12S-C13S
 1.54 with sigma of 0.02
 C14S-C13S
 1.54 with sigma of 0.02
 C11S-C13S
 2.43 with sigma of 0.02
 C14S-C12S
 2.43 with sigma of 0.02
 O1S-C12S
 2.37 with sigma of 0.02
 O1S-C13S
 2.37 with sigma of 0.02
4. Rigid bond restraints
 C17D, C18D, C19D, C20D, C21D, C22D, C23D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17G, C18G, C19G, C20G, C21G, C22G, C23G
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19B, C20B, C21B, C22B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C19F, C20F, C21F, C22F
 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 C18D \\sim C19D \\sim C20D \\sim C21D \\sim C22D \\sim C23D: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C17G \\sim C18G \\sim C19G \\sim C20G \\sim C21G \\sim C22G \\sim C23G: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C19B \\sim C20B \\sim C21B \\sim C22B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C19F \\sim C20F \\sim C21F \\sim C22F: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Uanis(C17C) \\sim Ueq, Uanis(C18C) \\sim Ueq, Uanis(C19C) \\sim Ueq,
Uanis(C20C) \\sim Ueq, Uanis(C21C) \\sim Ueq, Uanis(C22C) \\sim Ueq,
Uanis(C23C) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C19A) = Uanis(C19E)
Uanis(C20A) = Uanis(C20E)
Uanis(C21A) = Uanis(C21E)
Uanis(C22A) = Uanis(C22E)
Uanis(C23A) = Uanis(C23E)
Uanis(C19B) = Uanis(C19F) = Uanis(C20B) = Uanis(C20F)
Uanis(C21B) = Uanis(C21F)
Uanis(C22B) = Uanis(C22F)
Uanis(C17D) = Uanis(C17G)
Uanis(C18D) = Uanis(C18G)
Uanis(C19D) = Uanis(C19G)
Uanis(C20D) = Uanis(C20G)
Uanis(C21D) = Uanis(C21G)
Uanis(C22D) = Uanis(C22G)
Uanis(C23D) = Uanis(C23G)
Uanis(O1S) = Uanis(C14S) = Uanis(C11S) = Uanis(C12S) = Uanis(C13S)
6. Others
 Sof(H18C)=Sof(H18D)=Sof(C19E)=Sof(H19I)=Sof(H19J)=Sof(C20E)=Sof(H20I)=
 Sof(H20J)=Sof(C21E)=Sof(H21I)=Sof(H21J)=Sof(C22E)=Sof(H22J)=Sof(H22K)=
 Sof(C23E)=Sof(H23J)=Sof(H23K)=Sof(H23L)=1-FVAR(1)
 Sof(H18A)=Sof(H18B)=Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(C20A)=Sof(H20A)=
 Sof(H20B)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(C22A)=Sof(H22A)=Sof(H22B)=
 Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(H18G)=Sof(H18H)=Sof(C19F)=Sof(H19K)=Sof(H19L)=Sof(C20F)=Sof(H20K)=
 Sof(H20L)=Sof(C21F)=Sof(H21K)=Sof(H21L)=Sof(C22F)=Sof(H22L)=Sof(H22M)=
 Sof(H22N)=1-FVAR(2)
 Sof(H18E)=Sof(H18F)=Sof(C19B)=Sof(H19C)=Sof(H19D)=Sof(C20B)=Sof(H20C)=
 Sof(H20D)=Sof(C21B)=Sof(H21C)=Sof(H21D)=Sof(C22B)=Sof(H22C)=Sof(H22D)=
 Sof(H22E)=FVAR(2)
 Sof(H16E)=Sof(C17G)=Sof(H17I)=Sof(H17J)=Sof(C18G)=Sof(H18M)=Sof(H18N)=
 Sof(C19G)=Sof(H19M)=Sof(H19N)=Sof(C20G)=Sof(H20M)=Sof(H20N)=Sof(C21G)=
 Sof(H21M)=Sof(H21N)=Sof(C22G)=Sof(H22O)=Sof(H22P)=Sof(C23G)=Sof(H23M)=
 Sof(H23N)=Sof(H23O)=1-FVAR(3)
 Sof(H16D)=Sof(C17D)=Sof(H17G)=Sof(H17H)=Sof(C18D)=Sof(H18K)=Sof(H18L)=
 Sof(C19D)=Sof(H19G)=Sof(H19H)=Sof(C20D)=Sof(H20G)=Sof(H20H)=Sof(C21D)=
 Sof(H21G)=Sof(H21H)=Sof(C22D)=Sof(H22H)=Sof(H22I)=Sof(C23D)=Sof(H23G)=
 Sof(H23H)=Sof(H23I)=FVAR(3)
 Fixed Sof: O1S(0.25) C14S(0.25) H14A(0.25) H14B(0.25) C11S(0.25) H11A(0.25)
 H11B(0.25) C13S(0.25) H13A(0.25) H13B(0.25) C12S(0.25) H12E(0.25) H12F(0.25)
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:
 C8A(H8AA,H8AB), C8B(H8BA,H8BB), C8C(H8CA,H8CB), C8D(H8DA,H8DB), C15A(H15A,
 H15B), C15B(H15C,H15D), C15C(H15E,H15F), C15D(H15G,H15H), C17A(H17A,H17B),
 C17B(H17C,H17D), C17C(H17E,H17F), C17D(H17G,H17H), C17G(H17I,H17J), C18A(H18A,
 H18B), C18A(H18C,H18D), C18B(H18E,H18F), C18B(H18G,H18H), C18C(H18I,H18J),
 C18D(H18K,H18L), C18G(H18M,H18N), C19A(H19A,H19B), C19B(H19C,H19D), C19C(H19E,
 H19F), C19D(H19G,H19H), C19E(H19I,H19J), C19F(H19K,H19L), C19G(H19M,H19N),
 C20A(H20A,H20B), C20B(H20C,H20D), C20C(H20E,H20F), C20D(H20G,H20H), C20E(H20I,
 H20J), C20F(H20K,H20L), C20G(H20M,H20N), C21A(H21A,H21B), C21B(H21C,H21D),
 C21C(H21E,H21F), C21D(H21G,H21H), C21E(H21I,H21J), C21F(H21K,H21L), C21G(H21M,
 H21N), C22A(H22A,H22B), C22C(H22F,H22G), C22D(H22H,H22I), C22E(H22J,H22K),
 C22G(H22O,H22P), C14S(H14A,H14B), C11S(H11A,H11B), C13S(H13A,H13B), C12S(H12E,
 H12F)
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:
 C7A(H7AA,H7AB,H7AC), C7B(H7BA,H7BB,H7BC), C7C(H7CA,H7CB,H7CC), C7D(H7DA,H7DB,
 H7DC), C22B(H22C,H22D,H22E), C22F(H22L,H22M,H22N), C23A(H23A,H23B,H23C),
 C23C(H23D,H23E,H23F), C23D(H23G,H23H,H23I), C23E(H23J,H23K,H23L), C23G(H23M,
 H23N,H23O), C2S(H2SA,H2SB,H2SC)
;
_shelx_res_checksum              32168
_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 1.581
_oxdiff_exptl_absorpt_empirical_full_min 0.779