Cu site differentiation in tetracopper(i) sulfide clusters enables biomimetic N<sub>2</sub>O reduction.
Alayoglu, Pinar; Rathnayaka, Suresh C.; Chang, Tieyan; Wang, SuYin Grass; Chen, Yu-Sheng; Mankad, Neal P.; Chemical science 15 (2024) 13668–13675; doi:10.1039/d4sc00701h

data_1572466
_publ_section_title
;
 Cu site differentiation in tetracopper(i) sulfide clusters enables
 biomimetic N<sub>2</sub>O reduction.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              13668
_journal_page_last               13675
_journal_paper_doi               10.1039/d4sc00701h
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety
'C96 H84 Cu4 N4 P8 S, 2(F6 P), 6(C3 H6 O), H2 O'
_chemical_formula_sum            'C114 H122 Cu4 F12 N4 O7 P10 S'
_chemical_formula_weight         2484.07
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-07-31
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-09-06 deposited with the CCDC.	2024-08-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.9440(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.6516(7)
_cell_length_b                   27.2272(13)
_cell_length_c                   29.4109(14)
_cell_measurement_reflns_used    9443
_cell_measurement_temperature    77.15
_cell_measurement_theta_max      14.91
_cell_measurement_theta_min      2.29
_cell_volume                     11556.4(10)
_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_temperature      77.15
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.956
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.40633
_diffrn_reflns_av_R_equivalents  0.1146
_diffrn_reflns_av_unetI/netI     0.1137
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.956
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            199458
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        14.111
_diffrn_reflns_theta_max         18.292
_diffrn_reflns_theta_min         0.804
_exptl_absorpt_coefficient_mu    0.215
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.428
_exptl_crystal_description       plate
_exptl_crystal_F_000             5120
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.080
_refine_diff_density_max         0.780
_refine_diff_density_min         -0.516
_refine_diff_density_rms         0.127
_refine_ls_abs_structure_details
;
 Flack x determined using 11810 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.016(14)
_refine_ls_extinction_coef       0.0061(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   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1385
_refine_ls_number_reflns         41340
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0845
_refine_ls_R_factor_gt           0.0568
_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^)+(0.0401P)^2^+0.1630P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1400
_reflns_Friedel_coverage         0.938
_reflns_Friedel_fraction_full    0.968
_reflns_Friedel_fraction_max     0.898
_reflns_number_gt                31031
_reflns_number_total             41340
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00701h8.cif
_cod_data_source_block           s12_m
_cod_database_code               1572466
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2.a Free rotating group:
 O00Q(H00A,H00B)
2.b Aromatic/amide H refined with riding coordinates:
 N00L(H00L), N00M(H00M), N00R(H00R), C00Y(H00Y), N010(H010), C011(H011),
 C012(H012), C013(H013), C014(H014), C015(H015), C016(H016), C019(H019),
 C01F(H01F), C01G(H01G), C01H(H01H), C01I(H01I), C01J(H01J), C01K(H01K),
 C01L(H01L), C01M(H01M), C01P(H01P), C01Q(H01Q), C01R(H01R), C01S(H01S),
 C01T(H01T), C01U(H01U), C01V(H01V), C01Y(H01Y), C01Z(H01Z), C020(H020),
 C021(H021), C022(H022), C023(H023), C025(H025), C026(H026), C028(H028),
 C02A(H02A), C02B(H02B), C02C(H02C), C02D(H02D), C02E(H02E), C02F(H02F),
 C02G(H02G), C02H(H02H), C02I(H02I), C02J(H02J), C02L(H02L), C02N(H02N),
 C02O(H02O), C02P(H02P), C02Q(H02Q), C02R(H02R), C02S(H02S), C02T(H02T),
 C02U(H02U), C02V(H02V), C02W(H02W), C02X(H02X), C02Y(H02Y), C02Z(H02Z),
 C030(H030), C031(H031), C032(H032), C033(H033), C035(H035), C036(H036),
 C037(H037), C039(H039), C03A(H03A), C03B(H03B), C03C(H03C), C03E(H03E),
 C03I(H03I), C03J(H03J), C03K(H03K), C03M(H03M), C03N(H03N), C03O(H03O),
 C03Q(H03Q), C03S(H03S), C03U(H03U), C03V(H03V), C03X(H03X), C03Z(H03Z)
2.c Idealised Me refined as rotating group:
 C03D(H03R,H03T,H03W), C03P(H03D,H03F,H03G), C03R(H03H,H03L,H03P), C03Y(H03Y,H,
 HA), C041(H04J,H04K,H04L), C042(H04D,H04E,H04F), C043(H04A,H04B,H04C),
 C044(H04S,H04T,H04U), C045(H04M,H04N,H04O), C046(H04G,H04H,H04I), C047(H04P,
 H04Q,H04R), C048(H04V,H04W,H04X)
;
_shelx_res_checksum              77447
_olex2_submission_special_instructions 'No special instructions were received'