Monitoring structure and coordination chemistry of Co<sub>4</sub>O<sub>4</sub>-based oxygen evolution catalysts by nitrogen-14/-15 and cobalt-59 NMR spectroscopy.
Uhlig, Felix; Stammler, Michael B.; Meurer, Florian; Shenderovich, Ilya G.; Blahut, Jan; Wisser, Florian M.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 8541–8545; doi:10.1039/d4dt01273a

data_7715921
_publ_section_title
;
 Monitoring structure and coordination chemistry of
 Co<sub>4</sub>O<sub>4</sub>-based oxygen evolution catalysts by
 nitrogen-14/-15 and cobalt-59 NMR spectroscopy.
;
_journal_issue                   20
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              8541
_journal_page_last               8545
_journal_paper_doi               10.1039/d4dt01273a
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C27.75 H30.84 Co4 N4 O12, 0.5(C4 H6 N2)'
_chemical_formula_sum            'C30 H35 Co4 N5 O12'
_chemical_formula_weight         893.372
_space_group_crystal_system      orthorhombic
_space_group_IT_number           58
_space_group_name_Hall           '-P 2 2n'
_space_group_name_H-M_alt        'P n n m'
_symmetry_Int_Tables_number      58
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2f4w2k
_audit_creation_date             2022-06-30
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.06.10 svn.r3fa896fb for OlexSys, GUI svn.r6535)
;
_audit_update_record
;
2023-01-31 deposited with the CCDC.	2024-05-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.6668(2)
_cell_length_b                   13.8232(1)
_cell_length_c                   13.5182(1)
_cell_measurement_reflns_used    30562
_cell_measurement_temperature    123.00(10)
_cell_measurement_theta_max      74.4190
_cell_measurement_theta_min      3.8740
_cell_volume                     3675.03(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.17a (Rigaku OD, 2022)'
_computing_data_collection
'CrysAlisPro system (CCD 42.51a 64-bit (release 28-03-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.17a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.9997
_diffrn_measured_fraction_theta_max 0.9838
_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     21.00  90.00   0.50    3.00    --   63.22-125.00   0.00  138
  2  \w     26.00  64.00   0.50    3.00    --   63.22 -95.00 120.00   76
  3  \w     23.00  69.00   0.50    3.00    --   63.22-125.00  60.00   92
  4  \w     30.00  60.00   0.50    3.00    --   63.22 -95.00-180.00   60
  5  \w    -99.00 -63.00   0.50    3.00    --  -63.82 -15.00   0.00   72
  6  \w    -60.00 -32.00   0.50    3.00    --  -63.82 -15.00   0.00   56
  7  \w    -73.00 -32.00   0.50    3.00    --  -63.82 -15.00 120.00   82
  8  \w   -109.00 -76.00   0.50    3.00    --  -63.82 -15.00  90.00   66
  9  \w    -64.00 -37.00   0.50    3.00    --  -63.82 -15.00  90.00   54
 10  \w   -108.00 -76.00   0.50    3.00    --  -63.82 -15.00 120.00   64
 11  \w   -105.00 -43.00   0.50    3.00    --  -63.82 -15.00-150.00  124
 12  \w   -102.00 -31.00   0.50    3.00    --  -73.72 125.00-180.00  142
 13  \w   -102.00 -68.00   0.50    3.00    --  -73.72 125.00  30.00   68
 14  \w    -65.00 -31.00   0.50    3.00    --  -73.72 125.00  30.00   68
 15  \w   -106.00 -36.00   0.50   10.00    --  -78.25 124.00 -59.96  140
 16  \w   -122.00 -97.00   0.50   10.00    --  -78.25 -54.00  67.03   50
 17  \w   -105.00 -43.00   0.50   10.00    --  -78.25 121.00 -18.58  124
 18  \w   -112.00 -86.00   0.50   10.00    --  -78.25 -81.00 144.48   52
 19  \w   -103.00 -41.00   0.50   10.00    --  -78.25 117.00 -89.10  124
 20  \w   -106.00 -80.00   0.50   10.00    --  -78.25 -82.00-106.59   52
 21  \w   -110.00 -42.00   0.50   10.00    --  -78.25 132.00-177.94  136
 22  \w    -70.00 -44.00   0.50   10.00    --  -78.25 121.00 176.06   52
 23  \w   -101.00 -49.00   0.50   10.00    --  -78.25 114.00 120.46  104
 24  \w   -102.00 -49.00   0.50   10.00    --  -78.25 116.00 158.48  106
 25  \w   -110.00 -50.00   0.50   10.00    --  -78.25 132.00-142.89  120
 26  \w   -101.00 -40.00   0.50   10.00    --  -78.25 118.00  58.10  122
 27  \w   -105.00 -76.00   0.50   10.00    --  -78.25 121.00 176.06   58
 28  \w   -108.00 -82.00   0.50   10.00    --  -78.25 -78.00 -72.20   52
 29  \w     48.00 113.00   0.50   10.00    --   79.75  -1.00  17.75  130
 30  \w     64.00 107.00   0.50   10.00    --   79.75  22.00  69.52   86
 31  \w     41.00 104.00   0.50   10.00    --   79.75-116.00  86.97  126
 32  \w     52.00 121.00   0.50   10.00    --   79.75  17.00 -93.83  138
 33  \w     50.00  77.00   0.50   10.00    --   79.75 -87.00-177.92   54
 34  \w     43.00  87.00   0.50   10.00    --   79.75 -94.00  86.83   88
 35  \w     73.00 114.00   0.50   10.00    --   79.75  23.00-160.29   82
 36  \w     74.00 117.00   0.50   10.00    --   79.75  21.00 127.45   86
 37  \w     51.00  81.00   0.50   10.00    --   79.75  -4.00-102.36   60
 38  \w     61.00 105.00   0.50   10.00    --   79.75  20.00 -27.70   88
 39  \w     47.00 120.00   0.50   10.00    --   79.75   7.00 118.62  146
 40  \w     88.00 124.00   0.50   10.00    --   79.75  34.00 -23.33   72
 41  \w     58.00  83.00   0.50   10.00    --   79.75 -88.00  -0.95   50
 42  \w     45.00 110.00   0.50   10.00    --   79.75-129.00 171.22  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0446479000
_diffrn_orient_matrix_UB_12      -0.0281926000
_diffrn_orient_matrix_UB_13      -0.0890717000
_diffrn_orient_matrix_UB_21      0.0180012000
_diffrn_orient_matrix_UB_22      -0.0963456000
_diffrn_orient_matrix_UB_23      0.0509499000
_diffrn_orient_matrix_UB_31      -0.0618264000
_diffrn_orient_matrix_UB_32      -0.0485424000
_diffrn_orient_matrix_UB_33      -0.0493547000
_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  0.0438
_diffrn_reflns_av_unetI/netI     0.0159
_diffrn_reflns_Laue_measured_fraction_full 0.9997
_diffrn_reflns_Laue_measured_fraction_max 0.9838
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            60800
_diffrn_reflns_point_group_measured_fraction_full 0.9997
_diffrn_reflns_point_group_measured_fraction_max 0.9838
_diffrn_reflns_theta_full        67.6840
_diffrn_reflns_theta_max         75.92
_diffrn_reflns_theta_min         3.91
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.459
_exptl_absorpt_correction_T_max  0.845
_exptl_absorpt_correction_T_min  0.152
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.17a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark green'
_exptl_crystal_density_diffrn    1.615
_exptl_crystal_description       needle
_exptl_crystal_F_000             1787.025
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.5653
_refine_diff_density_min         -0.3229
_refine_diff_density_rms         0.0612
_refine_ls_d_res_high            0.7948
_refine_ls_d_res_low             11.3091
_refine_ls_goodness_of_fit_ref   1.0566
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    57
_refine_ls_number_parameters     340
_refine_ls_number_reflns         3938
_refine_ls_number_restraints     420
_refine_ls_restrained_S_all      0.9998
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0322
_refine_ls_shift/su_max          0.0040
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0520P)^2^+2.0534P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0898
_refine_ls_wR_factor_ref         0.0918
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              24
_reflns_limit_h_min              0
_reflns_limit_k_max              17
_reflns_limit_k_min              0
_reflns_limit_l_max              16
_reflns_limit_l_min              0
_reflns_number_gt                3602
_reflns_number_total             3938
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4dt01273a2.cif
_cod_data_source_block           Co4O4OAc4Py4
_cod_depositor_comments          'Adding full bibliography for 7715921.cif.'
_cod_database_code               7715921
_chemical_oxdiff_formula         'Co4 O12 C28 N4'
_chemical_oxdiff_usercomment     '123 K'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-C3 = N2-C7
 1.33 with sigma of 0.02
 C3-C1 = C6-C7
 1.38 with sigma of 0.02
 C1-C5 = C5-C6
 1.37 with sigma of 0.02
 N2-C1
 2.4 with sigma of 0.04
 N2-C6
 2.39 with sigma of 0.04
 C3-C5
 2.36 with sigma of 0.04
 C1-C6
 2.35 with sigma of 0.04
 C5-C7
 2.37 with sigma of 0.04
 C00Q-C00W \\sim C00Q-C00X
 with sigma of 0.04
 N00E-C4
 with sigma of 0.02
 N00E-C00K
 with sigma of 0.02
 Co01-N00E
 with sigma of 0.02
 C00R-C00T \\sim C4-C00U
 with sigma of 0.04
 C00Q-C00T \\sim C00Q-C00U
 with sigma of 0.02
 C00R-C00W \\sim C4-C00X
 with sigma of 0.02
 Co01-C00R \\sim Co01-C4
 with sigma of 0.04
 N00E-C00X
 with sigma of 0.04
 C00T-C00W \\sim C00U-C00X
 with sigma of 0.02
 C00K-C00R \\sim C00K-C4
 with sigma of 0.04
 N2-C3 \\sim N2-C7
 with sigma of 0.02
 C3-C1 \\sim C1-C5 \\sim C5-C6 \\sim C6-C7
 with sigma of 0.02
 N2-C6 \\sim N2-C1
 with sigma of 0.04
 C5-C7 \\sim C5-C3 \\sim C6-C1 \\sim C7-C3
 with sigma of 0.04
 N2-C3 \\sim N2-C3a
 with sigma of 0.02
 N2-C7 \\sim N2-C7a
 with sigma of 0.02
 C3-C1 \\sim C3a-C1a
 with sigma of 0.02
 C1-C5 \\sim C1a-C5a
 with sigma of 0.02
 C5-C6 \\sim C5a-C6a
 with sigma of 0.02
 C6-C7 \\sim C6a-C7a
 with sigma of 0.02
 N2-C1 \\sim N2-C1a
 with sigma of 0.04
 N2-C6 \\sim N2-C6a
 with sigma of 0.04
 C3-C5 \\sim C3a-C5a
 with sigma of 0.04
 C1-C6 \\sim C1a-C6a
 with sigma of 0.04
 C5-C7 \\sim C5a-C7a
 with sigma of 0.04
3. Restrained planarity
 N2, C3, C1, C5, C6, C7
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
C00K \\sim C00Q \\sim C00R \\sim C00T \\sim C00W \\sim N00E \\sim C4 \\sim C00X
\\sim C00U: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
N2 \\sim C3 \\sim C1 \\sim C5 \\sim C6 \\sim C7: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
N2 \\sim C3 \\sim C1 \\sim C5 \\sim C6 \\sim C7 \\sim C3a \\sim C1a \\sim C5a
\\sim C6a \\sim C7a: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.01 within 2A
: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C00K, C00Q, C00T, C00W, C00R
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C00W, C00T, C00R, C00K, C00Q
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N2, C3, C1, C5, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C4)=Sof(C00X)=Sof(C00U)=Sof(H00K)=Sof(H00g)=Sof(H4)=Sof(H00X)=Sof(H00U)=1-
 FVAR(1)
 Sof(N00D)=Sof(C00R)=Sof(C00T)=Sof(C00W)=Sof(H00K)=Sof(H00Q)=Sof(H00R)=
 Sof(H00T)=Sof(H00W)=Sof(H00R)=FVAR(1)
 Fixed Sof: C00S(0.5) C2(0.5) C1(0.25) C3(0.5) C5(0.5) C6(0.5) H00i(0.5)
 H00l(0.5) H00m(0.5) H00S(0.5) H2(0.5) H1(0.25) H3a(0.5) H3b(0.5) H3c(0.5)
 H5(0.5) H6a(0.5) H6b(0.5) H6c(0.5) H00a(0.5) H00b(0.5) H3a(0.5) H3b(0.5)
 H3c(0.5) C7a(0.25) C3(0.25) C3a(0.25) C7(0.25) C1(0.25) C5(0.125) C6(0.25)
 C1a(0.25) C5a(0.25) C6a(0.25) H3(0.25) H7(0.25) H6(0.25) H1(0.25) H3a(0.25)
 H7a(0.25) H6a(0.25) H5a(0.25) H1a(0.25) H5(0.125)
7.a Me refined with riding coordinates:
 C00N(H00d,H00e,H00f)
7.b Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00J(H00J), C00K(H00K), C00O(H00O), C00Q(H00Q), C00Q(H00g),
 C00T(H00T), C00W(H00W), C4(H4), C00X(H00X), C00U(H00U), C3(H3), C7(H7), C6(H6),
  C1(H1), C3a(H3a), C7a(H7a), C6a(H6a), C5a(H5a), C1a(H1a), C5(H5), C00R(H00R)
7.c Idealised Me refined as rotating group:
 C00L(H00a,H00b,H00c), C00M(H00i,H00l,H00m)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.0
_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 3.021
_oxdiff_exptl_absorpt_empirical_full_min 0.414