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_7719915
_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
'2(C164 H156 Cu22 N8 P12), 6(Cl O4), 3(C2 H3 N)'
_chemical_formula_sum            'C334 H321 Cl6 Cu44 N19 O24 P24'
_chemical_formula_weight         8736.82
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_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                74.0600(10)
_cell_angle_beta                 74.5490(10)
_cell_angle_gamma                81.8620(10)
_cell_formula_units_Z            2
_cell_length_a                   23.1531(2)
_cell_length_b                   29.1303(3)
_cell_length_c                   36.0582(3)
_cell_measurement_reflns_used    115366
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      76.9990
_cell_measurement_theta_min      2.2810
_cell_volume                     22478.0(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     -8.00  59.00   0.50   15.00    --   47.12 -54.00 -10.00  134
  2  \w     48.00  96.00   0.50   15.00    --   47.12-125.00  30.00   96
  3  \w     36.00  61.00   0.50   40.00    --  108.56 -54.00 -10.00   50
  4  \w     42.00  83.00   0.50   40.00    --  108.56 -77.00 -60.00   82
  5  \w     81.00 110.00   0.50   40.00    --  108.56-125.00   0.00   58
  6  \w     83.00 109.00   0.50   40.00    --  108.56-125.00 -30.00   52
  7  \w     64.00  90.00   0.50   40.00    --  108.56-161.00-142.19   52
  8  \w    106.00 136.00   0.50   40.00    --  108.56-161.00-142.19   60
  9  \w     82.00 107.00   0.50   40.00    --  108.56-104.00-127.67   50
 10  \w     69.00 107.00   0.50   40.00    --  108.56-106.00-155.20   76
 11  \w     46.00  71.00   0.50   40.00    --  108.56 -61.00 -60.00   50
 12  \w     40.00  66.00   0.50   40.00    --  108.56 -61.00   0.00   52
 13  \w     43.00 107.00   0.50   40.00    --  108.56-106.00  15.44  128
 14  \w     74.00 105.00   0.50   40.00    --  108.56 -77.00  90.00   62
 15  \w     81.00 106.00   0.50   40.00    --  108.56 -77.00 150.00   50
 16  \w     50.00 111.00   0.50   40.00    --  108.56-125.00 144.71  122
 17  \w     42.00 112.00   0.50   40.00    --  108.56-131.00  62.32  140
 18  \w     36.00 102.00   0.50   40.00    --  108.56-125.00  90.00  132
 19  \w     36.00  99.00   0.50   40.00    --  108.56-125.00 120.00  126
 20  \w     36.00  65.00   0.50   40.00    --  108.56-125.00   0.00   58
 21  \w     36.00 104.00   0.50   40.00    --  108.56-106.00 -58.84  136
 22  \w     36.00  99.00   0.50   40.00    --  108.56 -94.00-120.00  126
 23  \w     42.00  98.00   0.50   40.00    --  108.56-103.00-171.32  112
 24  \w     39.00  64.00   0.50   40.00    --  108.56-104.00-127.67   50
 25  \w     36.00  61.00   0.50   40.00    --  108.56 -61.00 -90.00   50
 26  \w     93.00 170.00   0.50   40.00    --  108.56  30.00 -90.00  154
 27  \w    101.00 178.00   0.50   40.00    --  108.56  30.00-150.00  154
 28  \w     94.00 177.00   0.50   40.00    --  108.56  45.00-180.00  166
 29  \w    102.00 145.00   0.50   40.00    --  108.56  61.00  60.00   86
 30  \w     92.00 174.00   0.50   40.00    --  108.56  54.00 133.00  164
 31  \w     97.00 175.00   0.50   40.00    --  108.56  45.00  90.00  156
 32  \w     42.00 118.00   0.50   15.00    --   47.12  54.00 133.00  152
 33  \w     36.00  69.00   0.50   40.00    --  108.56 -61.00 150.00   66
 34  \w    -61.00  22.00   0.50   15.00    --  -47.12  54.00 133.00  166
 35  \w    -25.00  28.00   0.50   15.00    --  -47.12  19.00-120.00  106
 36  \w    -38.00 -13.00   0.50   15.00    --  -47.12 125.00 -90.00   50
 37  \w    -44.00 -17.00   0.50   40.00    --  -88.50  45.00 -90.00   54
 38  \w    -49.00 -24.00   0.50   40.00    --  -88.50  45.00-150.00   50
 39  \w    -84.00 -59.00   0.50   15.00    --  -47.12 125.00 -90.00   50
 40  \w    -84.00 -53.00   0.50   40.00    --  -88.50 125.00-150.00   62
 41  \w    -44.00 -18.00   0.50   40.00    --  -88.50  45.00  30.00   52
 42  \w    -51.00 -26.00   0.50   40.00    --  -88.50  45.00  60.00   50
 43  \w    -61.00 -19.00   0.50   40.00    --  -88.50  54.00 133.00   84
 44  \w   -117.00 -40.00   0.50   15.00    --  -47.12 -54.00 -10.00  154
 45  \w   -119.00 -94.00   0.50   15.00    --  -47.12-125.00 -60.00   50
 46  \w   -132.00-106.00   0.50   40.00    --  -88.50 -94.00 -60.00   52
 47  \w   -158.00-106.00   0.50   40.00    --  -88.50 -54.00 -10.00  104
 48  \w   -116.00 -84.00   0.50   15.00    --  -47.12-125.00  90.00   64
 49  \w   -110.00 -74.00   0.50   15.00    --  -47.12-125.00 120.00   72
;
_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      -0.0471529000
_diffrn_orient_matrix_UB_12      0.0390342000
_diffrn_orient_matrix_UB_13      -0.0141921000
_diffrn_orient_matrix_UB_21      -0.0111645000
_diffrn_orient_matrix_UB_22      -0.0300991000
_diffrn_orient_matrix_UB_23      -0.0261556000
_diffrn_orient_matrix_UB_31      -0.0494327000
_diffrn_orient_matrix_UB_32      -0.0247373000
_diffrn_orient_matrix_UB_33      0.0347619000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0576
_diffrn_reflns_av_unetI/netI     0.0471
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            300423
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        64.000
_diffrn_reflns_theta_max         64.000
_diffrn_reflns_theta_min         2.292
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.666
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88671
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange-yellow
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_description       rhombic?
_exptl_crystal_F_000             8776
_refine_diff_density_max         2.792
_refine_diff_density_min         -2.861
_refine_diff_density_rms         0.179
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     4071
_refine_ls_number_reflns         74430
_refine_ls_number_restraints     430
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0935
_refine_ls_R_factor_gt           0.0817
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1509P)^2^+76.6258P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2416
_refine_ls_wR_factor_ref         0.2510
_reflns_Friedel_coverage         0.000
_reflns_number_gt                59019
_reflns_number_total             74430
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02358k2.cif
_cod_data_source_block           Cu22
_cod_database_code               7719915
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N Cu P Cl'
_diffrn_oxdiff_digest_frames
;
01024aeb4f0390c0e80dfd3f556cbfd987000259c73
;
_diffrn_oxdiff_digest_hkl
;
010de6d16206ff738969d10abf743adededa45
;
_reflns_odcompleteness_completeness 99.75
_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
 Cl5-O19 = Cl5-O17 = Cl5-O18 = Cl5-O20
 1.5 with sigma of 0.02
 Cl4-O14 = Cl4-O16 = Cl4-O13 = Cl4-O15
 1.5 with sigma of 0.02
 Cl6-O21 = Cl6-O22 = Cl6-O24 = Cl6-O23
 1.5 with sigma of 0.02
 C329-C330
 1.45 with sigma of 0.01
 Cl5-O19 \\sim Cl5-O17 \\sim Cl5-O18 \\sim Cl5-O20
 with sigma of 0.02
 O19-O18 \\sim O17-O20 \\sim O19-O20 \\sim O17-O18 \\sim O19-O17 \\sim O18-O20
 with sigma of 0.04
 Cl4-O14 \\sim Cl4-O16 \\sim Cl4-O13 \\sim Cl4-O15
 with sigma of 0.02
 O14-O13 \\sim O16-O15 \\sim O14-O15 \\sim O16-O13 \\sim O14-O16 \\sim O13-O15
 with sigma of 0.04
 Cl6-O21 \\sim Cl6-O22 \\sim Cl6-O24 \\sim Cl6-O23
 with sigma of 0.02
 O21-O24 \\sim O22-O23 \\sim O21-O23 \\sim O22-O24 \\sim O21-O22 \\sim O24-O23
 with sigma of 0.04
3. Rigid bond restraints
 Cl3, Cl6, Cl5, Cl1, Cl2, Cl4, O9, O10, O11, O12, O21, O22, O23, O24, O17, O18,
  O19, O20, O1, O2, O3, O4, O5, O6, O7, O8, O13, O14, O15, O16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Cl3 \\sim Cl6 \\sim Cl5 \\sim Cl1 \\sim Cl2 \\sim Cl4 \\sim O9 \\sim O10 \\sim
O11 \\sim O12 \\sim O21 \\sim O22 \\sim O23 \\sim O24 \\sim O17 \\sim O18 \\sim
O19 \\sim O20 \\sim O1 \\sim O2 \\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim O7
\\sim O8 \\sim O13 \\sim O14 \\sim O15 \\sim O16: within 2A with sigma of 0.001
and sigma for terminal atoms of 0.002
Cl5 \\sim O17 \\sim O18 \\sim O19 \\sim O20: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Cl4 \\sim O13 \\sim O14 \\sim O15 \\sim O16: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Cl6 \\sim O21 \\sim O22 \\sim O23 \\sim O24: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
Uanis(O24) \\sim Ueq, Uanis(O21) \\sim Ueq, Uanis(O22) \\sim Ueq, Uanis(O23)
\\sim Ueq, Uanis(Cl6) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5. Rigid body (RIGU) restrains
 Cl1, O1, O2, O3, O4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl6, O21, O22, O23, O24
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl5, O17, O18, O19, O20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl4, O13, O14, O15, O16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C14(H14A,H14B), C27(H27A,H27B), C40(H40A,H40B), C53(H53A,H53B),
 C66(H66A,H66B), C79(H79A,H79B), C92(H92A,H92B), C105(H10A,H10B), C118(H11A,
 H11B), C131(H13A,H13B), C144(H14C,H14D), C165(H16J,H16K), C178(H17A,H17B),
 C191(H19A,H19B), C204(H20A,H20B), C217(H21A,H21B), C230(H23A,H23B), C243(H24A,
 H24B), C256(H25A,H25B), C269(H26A,H26B), C282(H28A,H28B), C295(H29A,H29B),
 C308(H30A,H30B)
6.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), C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C61(H61), C62(H62),
  C63(H63), C64(H64), C65(H65), C68(H68), C69(H69), C70(H70), C71(H71),
 C72(H72), C74(H74), C75(H75), C76(H76), C77(H77), C78(H78), C81(H81), C82(H82),
  C83(H83), C84(H84), C85(H85), C87(H87), C88(H88), C89(H89), C90(H90),
 C91(H91), C94(H94), C95(H95), C96(H96), C97(H97), C98(H98), C100(H100),
 C101(H101), C102(H102), C103(H103), C104(H104), C107(H107), C108(H108),
 C109(H109), C110(H110), C111(H111), C113(H113), C114(H114), C115(H115),
 C116(H116), C117(H117), C120(H120), C121(H121), C122(H122), C123(H123),
 C124(H124), C126(H126), C127(H127), C128(H128), C129(H129), C130(H130),
 C133(H133), C134(H134), C135(H135), C136(H136), C137(H137), C139(H139),
 C140(H140), C141(H141), C142(H142), C143(H143), C146(H146), C147(H147),
 C148(H148), C149(H149), C150(H150), C152(H152), C153(H153), C154(H154),
 C155(H155), C156(H156), C167(H167), C168(H168), C169(H169), C170(H170),
 C171(H171), C173(H173), C174(H174), C175(H175), C176(H176), C177(H177),
 C180(H180), C181(H181), C182(H182), C183(H183), C184(H184), C186(H186),
 C187(H187), C188(H188), C189(H189), C190(H190), C193(H193), C194(H194),
 C195(H195), C196(H196), C197(H197), C199(H199), C200(H200), C201(H201),
 C202(H202), C203(H203), C206(H206), C207(H207), C208(H208), C209(H209),
 C210(H210), C212(H212), C213(H213), C214(H214), C215(H215), C216(H216),
 C219(H219), C220(H220), C221(H221), C222(H222), C223(H223), C225(H225),
 C226(H226), C227(H227), C228(H228), C229(H229), C232(H232), C233(H233),
 C234(H234), C235(H235), C236(H236), C238(H238), C239(H239), C240(H240),
 C241(H241), C242(H242), C245(H245), C246(H246), C247(H247), C248(H248),
 C249(H249), C251(H251), C252(H252), C253(H253), C254(H254), C255(H255),
 C258(H258), C259(H259), C260(H260), C261(H261), C262(H262), C264(H264),
 C265(H265), C266(H266), C267(H267), C268(H268), C271(H271), C272(H272),
 C273(H273), C274(H274), C275(H275), C277(H277), C278(H278), C279(H279),
 C280(H280), C281(H281), C284(H284), C285(H285), C286(H286), C287(H287),
 C288(H288), C290(H290), C291(H291), C292(H292), C293(H293), C294(H294),
 C297(H297), C298(H298), C299(H299), C300(H300), C301(H301), C303(H303),
 C304(H304), C305(H305), C306(H306), C307(H307), C310(H310), C311(H311),
 C312(H312), C313(H313), C314(H314), C316(H316), C317(H317), C318(H318),
 C319(H319), C320(H320)
6.c Idealised Me refined as rotating group:
 C158(H15A,H15B,H15C), C160(H16A,H16B,H16C), C162(H16D,H16E,H16F), C164(H16G,
 H16H,H16I), C322(H32A,H32B,H32C), C324(H32D,H32E,H32F), C326(H32G,H32H,H32I),
 C328(H32J,H32K,H32L), C330(H33A,H33B,H33C), C334(H33D,H33E,H33F), C332(H33G,
 H33H,H33I)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              80085
_shelx_fab_checksum              92342
_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 1.745
_oxdiff_exptl_absorpt_empirical_full_min 0.711