High-nuclearity Cu hydride nanoclusters of Cu<sub>22</sub>H<sub>19</sub> and Cu<sub>20</sub>H<sub>13</sub> consolidated by an N-containing triphosphine ligand: synthesis, characterization and catalysis.
Ma, Meng-Xia; Zhou, Yi-Wu; Gui, Zi-Jian; Huang, Ting-Hong; Ni, Qing-Ling; Li, Shi-Ming; Gui, Liu-Cheng; Wang, Xiu-Jian; Dalton transactions (Cambridge, England : 2003)  (2025) –; doi:10.1039/d5dt02358k

data_7719914
_publ_section_title
;
 High-nuclearity Cu hydride nanoclusters of Cu<sub>22</sub>H<sub>19</sub>
 and Cu<sub>20</sub>H<sub>13</sub> consolidated by an N-containing
 triphosphine ligand: synthesis, characterization and catalysis.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d5dt02358k
_journal_year                    2025
_chemical_formula_moiety         'C162 H153 Cl4 Cu20 N7 P12, 3(Cl O4)'
_chemical_formula_sum            'C162 H153 Cl7 Cu20 N7 O12 P12'
_chemical_formula_weight         4280.50
_space_group_crystal_system      trigonal
_space_group_IT_number           167
_space_group_name_Hall           '-R 3 2"c'
_space_group_name_H-M_alt        'R -3 c :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-02-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-02-11 deposited with the CCDC.	2025-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            12
_cell_length_a                   26.2543(3)
_cell_length_b                   26.2543(3)
_cell_length_c                   113.8699(10)
_cell_measurement_reflns_used    26225
_cell_measurement_temperature    99.98(11)
_cell_measurement_theta_max      75.4890
_cell_measurement_theta_min      2.4790
_cell_volume                     67973.6(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(11)
_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 1.000
_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    -80.00  27.92   0.38    5.50    --  -43.18  96.00 -16.00  284
  2  \w    -39.00 -13.16   0.38   11.00    --  -90.25  34.00 146.00   68
  3  \w     35.00 103.78   0.38   11.00    --  109.26 -90.00 166.00  181
  4  \w     36.00 112.00   0.38   11.00    --  109.26-126.00 127.00  200
  5  \w     34.00  95.94   0.38    5.50    --   43.18-125.00   0.00  163
  6  \w    -51.00 -15.28   0.38   11.00    --  -90.25  45.00-180.00   94
  7  \w    -85.00 -16.22   0.38   11.00    --  -90.25 124.00   8.00  181
  8  \w     35.00  69.96   0.38   11.00    --  109.26 -61.00-150.00   92
  9  \w     80.00 176.90   0.38   11.00    --  109.26  77.00 -30.00  255
 10  \w     35.00  69.96   0.38   11.00    --  109.26 -61.00 -30.00   92
 11  \w     35.00  69.96   0.38   11.00    --  109.26 -61.00 -90.00   92
 12  \w     36.00  78.18   0.38   11.00    --  109.26 -94.00-180.00  111
 13  \w     71.00  96.08   0.38   11.00    --  109.26 -94.00-150.00   66
 14  \w     35.00  61.22   0.38   11.00    --  109.26 -61.00 -60.00   69
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0445016000
_diffrn_orient_matrix_UB_12      0.0209181000
_diffrn_orient_matrix_UB_13      -0.0022425000
_diffrn_orient_matrix_UB_21      -0.0429821000
_diffrn_orient_matrix_UB_22      -0.0600804000
_diffrn_orient_matrix_UB_23      -0.0054955000
_diffrn_orient_matrix_UB_31      -0.0275738000
_diffrn_orient_matrix_UB_32      -0.0233220000
_diffrn_orient_matrix_UB_33      0.0121606000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0391
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       132
_diffrn_reflns_limit_l_min       -92
_diffrn_reflns_number            85767
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        63.999
_diffrn_reflns_theta_max         63.999
_diffrn_reflns_theta_min         2.092
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.869
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43125
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_description       'cubic block'
_exptl_crystal_F_000             25788
_refine_diff_density_max         2.237
_refine_diff_density_min         -1.072
_refine_diff_density_rms         0.138
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     707
_refine_ls_number_reflns         12558
_refine_ls_number_restraints     214
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.0766
_refine_ls_R_factor_gt           0.0686
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1443P)^2^+460.8956P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2185
_refine_ls_wR_factor_ref         0.2259
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10489
_reflns_number_total             12558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02358k2.cif
_cod_data_source_block           Cu20
_cod_original_cell_volume        67973.6(17)
_cod_original_sg_symbol_H-M      'R -3 c'
_cod_database_code               7719914
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Cu C H O N P Cl '
_diffrn_oxdiff_digest_frames
;
01c2077d57c5a86828dd19ed541a518fe500027142a
;
_diffrn_oxdiff_digest_hkl
;
013a09ecc63577866e46e721902c752388b235
;
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 Cl4-O6 = Cl4-O5 = Cl4-O7 = Cl4-O8
 1.5 with sigma of 0.02
 Cl3-O1 = Cl3-O3 = Cl3-O4 = Cl3-O2
 1.5 with sigma of 0.02
 Cl4-O6 \\sim Cl4-O5 \\sim Cl4-O7 \\sim Cl4-O8
 with sigma of 0.02
 O6-O7 \\sim O5-O8 \\sim O6-O8 \\sim O5-O7 \\sim O6-O5 \\sim O7-O8
 with sigma of 0.04
 Cl3-O1 \\sim Cl3-O3 \\sim Cl3-O4 \\sim Cl3-O2
 with sigma of 0.02
 O1-O4 \\sim O3-O2 \\sim O1-O2 \\sim O3-O4 \\sim O1-O3 \\sim O4-O2
 with sigma of 0.04
3. Rigid bond restraints
 O5, O6, O7, O8, O1, O2, O3, O4, Cl1, Cl2, Cl4, Cl3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
O5 \\sim O6 \\sim O7 \\sim O8 \\sim O1 \\sim O2 \\sim O3 \\sim O4 \\sim Cl1
\\sim Cl2 \\sim Cl4 \\sim Cl3: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
Cl4 \\sim O5 \\sim O6 \\sim O7 \\sim O8: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Cl3 \\sim O1 \\sim O2 \\sim O3 \\sim O4: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(O4) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(O3) \\sim
Ueq, Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.02
5. Rigid body (RIGU) restrains
 Cl3, O1, O2, O3, O4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl4, O5, O6, O7, O8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Fixed Sof: Cl4(0.5) O5(0.5) O6(0.5) O7(0.5) O8(0.5) Cl3(0.5) O1(0.5) O2(0.5)
 O3(0.5) O4(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C14(H14A,H14B), C27(H27A,H27B), C40(H40A,H40B)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23),
  C24(H24), C25(H25), C26(H26), C29(H29), C30(H30), C31(H31), C32(H32),
 C33(H33), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C42(H42), C43(H43),
  C44(H44), C45(H45), C46(H46), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52)
7.c Idealised Me refined as rotating group:
 C023(H02A,H02B,H02C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              63881
_shelx_fab_checksum              97794
_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 2.091
_oxdiff_exptl_absorpt_empirical_full_min 0.557