Electrocatalytic nitrogen reduction to ammonia by atomically precise Cu<sub>6</sub> nanoclusters supported on graphene oxide.
Shehzad, Aamir; Cui, Chaonan; Cheng, Ran; Luo, Zhixun; Nanoscale 16 (2024) 14441–14447; doi:10.1039/d4nr01984a

data_1572127
_publ_section_title
;
 Electrocatalytic nitrogen reduction to ammonia by atomically precise
 Cu<sub>6</sub> nanoclusters supported on graphene oxide.
;
_journal_issue                   30
_journal_name_full               Nanoscale
_journal_page_first              14441
_journal_page_last               14447
_journal_paper_doi               10.1039/d4nr01984a
_journal_volume                  16
_journal_year                    2024
_chemical_formula_moiety         'C42 H54 Cu6 N12 S6'
_chemical_formula_sum            'C42 H54 Cu6 N12 S6'
_chemical_formula_weight         1300.57
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-27
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-07 deposited with the CCDC.	2024-07-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.3973(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.88670(14)
_cell_length_b                   13.06844(17)
_cell_length_c                   16.4807(2)
_cell_measurement_reflns_used    10120
_cell_measurement_temperature    170.0(4)
_cell_measurement_theta_max      76.3600
_cell_measurement_theta_min      4.2270
_cell_volume                     2525.77(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.0(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.963
_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     76.00 110.00   0.50    0.20    --  108.85-125.00-180.00   68
  2  \w     64.00  90.00   0.50    0.20    --  108.85-125.00-150.00   52
  3  \w    -13.00  78.00   0.50    0.05    --   46.54-100.00  60.00  182
  4  \w     70.00 101.00   0.50    0.20    --  108.85-100.00  60.00   62
  5  \w     40.00 108.00   0.50    0.20    --  108.85 -77.00  60.00  136
  6  \w     37.00  73.00   0.50    0.20    --  108.85 -61.00  60.00   72
  7  \w     42.00  67.00   0.50    0.20    --  108.85 -61.00 120.00   50
  8  \w     38.00  69.00   0.50    0.20    --  108.85 -61.00 150.00   62
  9  \w    144.00 178.00   0.50    0.20    --  108.85  15.00 150.00   68
 10  \w     92.00 169.00   0.50    0.20    --  108.85 100.00 165.00  154
 11  \w     92.00 178.00   0.50    0.20    --  108.85  61.00 120.00  172
 12  \w     91.00 126.00   0.50    0.20    --  108.85  15.00 150.00   70
 13  \w     24.00 118.00   0.50    0.05    --   46.54  77.00 150.00  188
 14  \w    -23.00   3.00   0.50    0.05    --  -46.54  19.00-180.00   52
 15  \w    -66.00 -36.00   0.50    0.20    -- -104.50  61.00-180.00   60
 16  \w    -61.00 -34.00   0.50    0.20    -- -104.50  61.00-120.00   54
 17  \w    -62.00 -34.00   0.50    0.20    -- -104.50  61.00 -60.00   56
 18  \w    -64.00 -31.00   0.50    0.20    -- -104.50  61.00 -30.00   66
 19  \w    -68.00 -35.00   0.50    0.20    -- -104.50  61.00   0.00   66
 20  \w    -66.00 -40.00   0.50    0.20    -- -104.50  61.00  30.00   52
 21  \w    -39.00  25.00   0.50    0.05    --  -46.54  38.00 -60.00  128
 22  \w   -132.00-100.00   0.50    0.20    -- -104.50 -30.00  60.00   64
 23  \w   -162.00-136.00   0.50    0.20    -- -104.50 -30.00  60.00   52
 24  \w   -154.00-129.00   0.50    0.20    -- -104.50-100.00  60.00   50
 25  \w    -29.00  -4.00   0.50    0.05    --  -46.54 100.00 165.00   50
 26  \w    -94.00 -69.00   0.50    0.20    -- -104.50 100.00 165.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0263590000
_diffrn_orient_matrix_UB_12      0.0442223000
_diffrn_orient_matrix_UB_13      0.0876986000
_diffrn_orient_matrix_UB_21      0.0524918000
_diffrn_orient_matrix_UB_22      -0.1030411000
_diffrn_orient_matrix_UB_23      0.0317227000
_diffrn_orient_matrix_UB_31      0.1175387000
_diffrn_orient_matrix_UB_32      0.0363450000
_diffrn_orient_matrix_UB_33      -0.0166022000
_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  0.0451
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            16989
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.485
_diffrn_reflns_theta_min         4.273
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.426
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69780
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.96a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.710
_exptl_crystal_description       block
_exptl_crystal_F_000             1320
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.462
_refine_diff_density_min         -0.424
_refine_diff_density_rms         0.080
_refine_ls_extinction_coef       0.00015(4)
_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   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         5169
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0322
_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^)+(0.0444P)^2^+0.9067P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0852
_refine_ls_wR_factor_ref         0.0885
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4575
_reflns_number_total             5169
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nr01984a2.cif
_cod_data_source_block           tx15462_auto
_cod_depositor_comments          'Adding full bibliography for 1572127.cif.'
_cod_original_cell_volume        2525.76(5)
_cod_database_code               1572127
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNOPClSAuCu
_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.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C12(H12A,H12B), C13(H13A,H13B), C19(H19A,H19B),
 C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C9(H9), C11(H11), C16(H16), C18(H18)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              6989
_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 1.518
_oxdiff_exptl_absorpt_empirical_full_min 0.700