Eight-electron copper-hydride nanoclusters: synthesis, structure, alloying chemistry and photoluminescence
Sun, Jing; Liu, Jiahe; Su, Hai-Feng; Li, Simin; Tang, Xiongkai; Xie, Zhenlang; Xu, Zhen; Jiang, Wenya; Wei, Jianyu; Gong, Xuekun; He, Ayisha; Wang, Song; Jiang, De-en; Zheng, Nanfeng; Shen, Hui; Chemical Science 16 (2025) 6392–6401; doi:10.1039/D4SC08547G

data_1574111
_publ_section_title
;
 Eight-electron copper-hydride nanoclusters: synthesis, structure,
 alloying chemistry and photoluminescence
;
_journal_issue                   15
_journal_name_full               'Chemical Science'
_journal_page_first              6392
_journal_page_last               6401
_journal_paper_doi               10.1039/D4SC08547G
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'C240 H180 Ag7.167 Cu39.833 F36 O24 P6 Se18, C H2 Cl2'
_chemical_formula_sum            'C241 H183 Ag7.17 Cl2 Cu39.83 F36 O24 P6 Se18'
_chemical_formula_weight         9128.98
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-04-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2024-11-13 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.3450(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.2386(2)
_cell_length_b                   36.7068(3)
_cell_length_c                   38.4701(3)
_cell_measurement_reflns_used    29241
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      64.7860
_cell_measurement_theta_min      3.9630
_cell_volume                     29673.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  27.00   1.00    1.00    --    0.00 -77.00  30.00   48
  2  \w    -64.00 -39.00   1.00    1.00    --    0.00-178.00 -60.00   25
  3  \w     69.00 106.00   1.00    2.50    --   87.81-125.00 -90.00   37
  4  \w    106.00 136.00   1.00    2.50    --   87.81  77.00-180.00   30
  5  \w     98.00 140.00   1.00    2.50    --   87.81 125.00  30.00   42
  6  \w    105.00 146.00   1.00    2.50    --   87.81  77.00-150.00   41
  7  \w     16.00 102.00   1.00    2.50    --   87.81 -94.00  60.00   86
  8  \w    -81.00  63.00   1.00    1.00    --    0.00   0.00  60.00  144
  9  \w    -20.00  29.00   1.00    1.00    --    0.00 -77.00-180.00   49
 10  \w     36.00 109.00   1.00    2.50    --   87.81 -45.00  90.00   73
 11  \w     99.00 126.00   1.00    2.50    --   87.81 125.00 120.00   27
 12  \w     68.00  94.00   1.00    2.50    --   87.81-125.00 -30.00   26
 13  \w     30.00  56.00   1.00    2.50    --   87.81 -94.00 120.00   26
 14  \w     27.00 113.00   1.00    2.50    --   87.81 -61.00 -90.00   86
 15  \w     60.00 103.00   1.00    2.50    --   87.81 -94.00 120.00   43
 16  \w     67.00 161.00   1.00    2.50    --   87.81  30.00 120.00   94
 17  \w    126.00 152.00   1.00    2.50    --   87.81 125.00   0.00   26
 18  \w    113.00 154.00   1.00    2.50    --   87.81  77.00 -30.00   41
 19  \w     86.00 113.00   1.00    2.50    --   87.81-125.00   0.00   27
 20  \w     62.00  98.00   1.00    2.50    --   87.81  61.00-120.00   36
 21  \w     98.00 123.00   1.00    2.50    --   87.81  45.00  90.00   25
 22  \w     99.00 147.00   1.00    2.50    --   87.81  45.00 -30.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0581592000
_diffrn_orient_matrix_UB_12      0.0255849000
_diffrn_orient_matrix_UB_13      -0.0041679000
_diffrn_orient_matrix_UB_21      -0.0417024000
_diffrn_orient_matrix_UB_22      -0.0307573000
_diffrn_orient_matrix_UB_23      -0.0183039000
_diffrn_orient_matrix_UB_31      -0.0160141000
_diffrn_orient_matrix_UB_32      -0.0127010000
_diffrn_orient_matrix_UB_33      0.0358394000
_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  0.0571
_diffrn_reflns_av_unetI/netI     0.0704
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            100372
_diffrn_reflns_point_group_measured_fraction_full 0.728
_diffrn_reflns_point_group_measured_fraction_max 0.728
_diffrn_reflns_theta_full        63.999
_diffrn_reflns_theta_max         63.999
_diffrn_reflns_theta_min         3.562
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.291
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61109
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    2.043
_exptl_crystal_description       block
_exptl_crystal_F_000             17492
_exptl_crystal_size_max          0.199
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.107
_refine_diff_density_max         4.397
_refine_diff_density_min         -1.462
_refine_diff_density_rms         0.169
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.134(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3452
_refine_ls_number_reflns         35881
_refine_ls_number_restraints     878
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0750
_refine_ls_R_factor_gt           0.0605
_refine_ls_shift/su_max          0.064
_refine_ls_shift/su_mean         0.006
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1053P)^2^+0.1187P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1556
_refine_ls_wR_factor_ref         0.1652
_reflns_Friedel_coverage         0.458
_reflns_Friedel_fraction_full    0.458
_reflns_Friedel_fraction_max     0.458
_reflns_number_gt                29859
_reflns_number_total             35881
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08547g2.cif
_cod_data_source_block           xl-4-20210425-j15_auto
_cod_depositor_comments
'Adding full bibliography for 1574111--1574112.cif.'
_cod_database_code               1574111
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.406
_shelx_estimated_absorpt_t_min   0.234
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.866(10)
 0.134(10)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Shared sites
{Ag32, Cu32}
4. Uiso/Uaniso restraints and constraints
Ag2 \\sim Ag7 \\sim Ag67: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
C10 \\sim C161 \\sim C207 \\sim C206 \\sim C205 \\sim C204: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C85 \\sim C86 \\sim C87 \\sim C48 \\sim C209 \\sim C45: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C82 \\sim C179 \\sim C57 \\sim C180 \\sim C84 \\sim C83: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C128 \\sim C142 \\sim C210 \\sim C69 \\sim C144 \\sim C143: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C167 \\sim C168 \\sim C13 \\sim C211 \\sim C169 \\sim C166: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C195 \\sim C191 \\sim C158 \\sim C114 \\sim C115 \\sim C198: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C107 \\sim C223 \\sim C224 \\sim C64 \\sim C109 \\sim C108: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O94 \\sim C81 \\sim O93 \\sim C75: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C238 \\sim C232 \\sim C231 \\sim C138 \\sim C236 \\sim C237: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C33 \\sim C61 \\sim C31 \\sim C63 \\sim C28 \\sim C34: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C47 \\sim C35 \\sim C24 \\sim C66 \\sim C59 \\sim C41: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C235 \\sim C141 \\sim C140 \\sim C80 \\sim C79 \\sim C58: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C229 \\sim C118 \\sim C116 \\sim C117 \\sim C176 \\sim C36: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C201 \\sim C53 \\sim C202 \\sim C171 \\sim C170 \\sim C52: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C68 \\sim C181 \\sim C182 \\sim C183 \\sim C203 \\sim C65: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C192 \\sim C3 \\sim C157 \\sim C155 \\sim C156 \\sim C4: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C196 \\sim C197 \\sim C9 \\sim C6 \\sim C113 \\sim C67: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C147 \\sim C102 \\sim C103 \\sim C104 \\sim C145 \\sim C146: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C92 \\sim C139 \\sim C88 \\sim C89 \\sim C90 \\sim C91: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Ag67 \\sim C122 \\sim C54 \\sim C21 \\sim C208 \\sim C123 \\sim C121: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C22 \\sim C51 \\sim C105 \\sim C213 \\sim C212 \\sim C49: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C212 \\sim C213 \\sim C105 \\sim C51 \\sim C22 \\sim C49: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C174 \\sim C94 \\sim C93 \\sim C95 \\sim C175 \\sim C38: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C20 \\sim C19 \\sim C18 \\sim C17 \\sim C132 \\sim C131: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(Cu25) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Ag2) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Ag67) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Cu6) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Cu4) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Cu5) \\sim Ueq, Uanis(Cu1) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(F10) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F32) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(Ag24) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Ag32) = Uanis(Cu32)
5. Others
 Fixed Sof: Ag24(0.5) Ag26(0.66667) Ag22(0.66666) Ag23(0.5) Ag1(0.66667)
 Ag32(0.33333) Ag36(0.5) Ag52(0.66667) Ag53(0.5) Ag61(0.5) Cu64(0.66667)
 Ag67(0.33333) Cu70(0.5) Cu71(0.5) Cu72(0.5) Cu(0.66667) Ag7(0.33333) Cu4(0.5)
 Cu6(0.33333) Cu25(0.5) Cu8(0.33333) Ag2(0.66666) Cu5(0.33333) Cu1(0.33333)
 Cu32(0.66667) Ag3(0.33333)
6.a Secondary CH2 refined with riding coordinates:
 C241(H24A,H24B)
6.b Aromatic/amide H refined with riding coordinates:
 C218(H218), C219(H219), C220(H220), C221(H221), C222(H222), C80(H80),
 C86(H86), C94(H94), C104(H104), C122(H122), C109(H109), C123(H123), C90(H90),
 C88(H88), C112(H112), C118(H118), C115(H115), C126(H126), C102(H102), C83(H83),
  C97(H97), C96(H96), C110(H110), C87(H87), C117(H117), C91(H91), C99(H99),
 C120(H120), C95(H95), C125(H125), C84(H84), C107(H107), C92(H92), C101(H101),
 C140(H140), C150(H150), C165(H165), C144(H144), C175(H175), C174(H174),
 C180(H180), C145(H145), C185(H185), C141(H141), C173(H173), C151(H151),
 C152(H152), C143(H143), C155(H155), C162(H162), C142(H142), C158(H158),
 C135(H135), C183(H183), C177(H177), C184(H184), C164(H164), C139(H139),
 C176(H176), C167(H167), C136(H136), C231(H231), C232(H232), C238(H238),
 C237(H237), C236(H236), C171(H171), C153(H153), C147(H147), C186(H186),
 C169(H169), C134(H134), C132(H132), C146(H146), C172(H172), C137(H137),
 C181(H181), C157(H157), C163(H163), C187(H187), C179(H179), C168(H168),
 C178(H178), C190(H190), C22(H22), C192(H192), C34(H34), C25(H25), C65(H65),
 C29(H29), C30(H30), C53(H53), C32(H32), C36(H36), C57(H57), C37(H37),
 C193(H193), C39(H39), C40(H40), C42(H42), C43(H43), C38(H38), C45(H45), C5(H5),
  C47(H47), C48(H48), C49(H49), C50(H50), C51(H51), C54(H54), C55(H55),
 C59(H59), C60(H60), C61(H61), C11(H11), C63(H63), C64(H64), C66(H66), C67(H67),
  C195(H195), C69(H69), C8(H8), C20(H20), C12(H12), C14(H14), C15(H15),
 C13(H13), C17(H17), C31(H31), C4(H4), C6(H6), C26(H26), C35(H35), C16(H16),
 C58(H58), C19(H19), C7(H7), C9(H9), C52(H52), C68(H68), C3(H3), C191(H191),
 C41(H41), C18(H18), C21(H21), C23(H23), C10(H10), C33(H33), C206(H206),
 C209(H209), C196(H196), C207(H207), C227(H227), C233(H233), C203(H203),
 C197(H197), C208(H208), C214(H214), C210(H210), C211(H211), C204(H204),
 C200(H200), C213(H213), C234(H234), C235(H235), C223(H223), C225(H225),
 C201(H201), C229(H229), C212(H212), C205(H205), C217(H217), C198(H198),
 C230(H230), C202(H202), C226(H226), C224(H224), C215(H215), C239(H239),
 C240(H240)
6.c Fitted hexagon refined as free rotating group:
 C78(C218,C219,C220,C221,C222), C138(C231,C232,C238,C237,C236)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              22569
_shelx_fab_checksum              33985
_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 1.732
_oxdiff_exptl_absorpt_empirical_full_min 0.781