Structural and reactivity investigations using organo-copper(i) and zinc(ii) complexes with hydrogen and carbon dioxide.
Cowie, Bradley E.; Phanopoulos, Andreas; Shaffer, Milo S. P.; Williams, Charlotte K.; Chemical science 17 (2026) 564–578; doi:10.1039/d5sc05666g

data_1576721
_publ_section_title
;
 Structural and reactivity investigations using organo-copper(i) and
 zinc(ii) complexes with hydrogen and carbon dioxide.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              564
_journal_page_last               578
_journal_paper_doi               10.1039/d5sc05666g
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C100 H89 Cu5 P8, 3(C6 H6)'
_chemical_formula_sum            'C118 H107 Cu5 P8'
_chemical_formula_weight         2090.49
_chemical_name_common            012bec21-bec
_chemical_name_systematic        '[Cu5(u-H)(u3-H)2(dppm')2(dppm)2]'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-04-12 deposited with the CCDC.	2025-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.0510(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8877(2)
_cell_length_b                   14.8052(2)
_cell_length_c                   44.2531(6)
_cell_measurement_reflns_used    30503
_cell_measurement_temperature    150.01(13)
_cell_measurement_theta_max      75.9270
_cell_measurement_theta_min      3.5630
_cell_volume                     10330.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.964
_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     -3.00  23.00   1.00    5.00    --  -42.66  19.00-180.00   26
  2  \w     -5.00  28.00   1.00    5.00    --  -42.66  19.00 -90.00   33
  3  \w      0.00  30.00   1.00    5.00    --  -42.66  19.00 150.00   30
  4  \w    -22.00  28.00   1.00    5.00    --  -42.66  38.00 120.00   50
  5  \w     -5.00  27.00   1.00    5.00    --  -42.66  19.00  60.00   32
  6  \w     -5.00  33.00   1.00    5.00    --  -42.66  19.00-150.00   38
  7  \w     85.00 128.00   1.00    5.00    --   42.66 178.00-150.00   43
  8  \w     93.00 125.00   1.00   20.00    --  111.00 -77.00  60.00   32
  9  \w     44.00  70.00   1.00   20.00    --  111.00 -45.00 120.00   26
 10  \w     60.00  89.00   1.00   20.00    --  111.00 -61.00  60.00   29
 11  \w     39.00  66.00   1.00   20.00    --  111.00 -95.00   0.00   27
 12  \w     68.00  94.00   1.00   20.00    --  111.00 -95.00   0.00   26
 13  \w     58.00  91.00   1.00   20.00    --  111.00 -61.00-180.00   33
 14  \w     40.00  65.00   1.00   20.00    --  111.00 -45.00  60.00   25
 15  \w     40.00  67.00   1.00   20.00    --  111.00 -45.00  90.00   27
 16  \w     43.00  69.00   1.00   20.00    --  111.00 -45.00-180.00   26
 17  \w    144.00 173.00   1.00   20.00    --  111.00  77.00 150.00   29
 18  \w    139.00 178.00   1.00   20.00    --  111.00  77.00  90.00   39
 19  \w     64.00  89.00   1.00   20.00    --  111.00 -61.00  90.00   25
 20  \w     66.00  91.00   1.00   20.00    --  111.00 -61.00 -90.00   25
 21  \w    110.00 137.00   1.00   20.00    --  111.00  77.00  90.00   27
 22  \w     45.00 108.00   1.00   20.00    --  111.00 -77.00  30.00   63
 23  \w    113.00 172.00   1.00   20.00    --  111.00  77.00-180.00   59
 24  \w     44.00  72.00   1.00   20.00    --  111.00 -45.00  30.00   28
 25  \w     50.00  76.00   1.00   20.00    --  111.00 -61.00-120.00   26
 26  \w    118.00 172.00   1.00   20.00    --  111.00  45.00 -30.00   54
 27  \w     44.00  70.00   1.00   20.00    --  111.00 -45.00 150.00   26
 28  \w    106.00 174.00   1.00   20.00    --  111.00 125.00  60.00   68
 29  \w    -19.00  23.00   1.00    5.00    --  -42.66  38.00   0.00   42
 30  \w      2.00  27.00   1.00    5.00    --  -42.66  19.00 -60.00   25
 31  \w    -22.00   3.00   1.00    5.00    --  -42.66  38.00 150.00   25
 32  \w    -44.00 -18.00   1.00    5.00    --  -42.66  57.00  60.00   26
 33  \w      2.00  27.00   1.00    5.00    --  -42.66  57.00  60.00   25
 34  \w     21.00  48.00   1.00    5.00    --   42.66 -99.00-150.00   27
 35  \w     63.00 127.00   1.00    5.00    --   42.66 178.00  30.00   64
 36  \w     98.00 124.00   1.00   20.00    --  111.00-141.00 154.63   26
 37  \w     42.00  68.00   1.00   20.00    --  111.00-141.00 154.63   26
 38  \w     67.00 108.00   1.00   20.00    --  111.00-102.00 -90.58   41
 39  \w    100.00 144.00   1.00   20.00    --  111.00  30.00  60.00   44
 40  \w     61.00  90.00   1.00   20.00    --  111.00-125.00  60.00   29
 41  \w    153.00 178.00   1.00   20.00    --  111.00  45.00 -90.00   25
 42  \w    125.00 151.00   1.00   20.00    --  111.00 125.00 120.00   26
 43  \w     40.00  65.00   1.00   20.00    --  111.00 -45.00  30.00   25
 44  \w    126.00 155.00   1.00   20.00    --  111.00  45.00 -60.00   29
 45  \w     81.00 107.00   1.00   20.00    --  111.00 -99.00-145.00   26
 46  \w     90.00 178.00   1.00   20.00    --  111.00  30.00-120.00   88
 47  \w     46.00  63.00   1.00   20.00    --  111.00-125.00-150.00   17
;
_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      0.0402509000
_diffrn_orient_matrix_UB_12      -0.0129843000
_diffrn_orient_matrix_UB_13      -0.0296480000
_diffrn_orient_matrix_UB_21      0.0393323000
_diffrn_orient_matrix_UB_22      0.0950650000
_diffrn_orient_matrix_UB_23      0.0037219000
_diffrn_orient_matrix_UB_31      0.0799386000
_diffrn_orient_matrix_UB_32      -0.0402317000
_diffrn_orient_matrix_UB_33      0.0183777000
_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  0.0594
_diffrn_reflns_av_unetI/netI     0.0518
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -54
_diffrn_reflns_number            99101
_diffrn_reflns_point_group_measured_fraction_full 0.718
_diffrn_reflns_point_group_measured_fraction_max 0.685
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.462
_diffrn_reflns_theta_min         3.092
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.674
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96178
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       block
_exptl_crystal_F_000             4320
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.088
_exptl_transmission_factor_max   1.00000
_exptl_transmission_factor_min   0.96178
_refine_diff_density_max         0.401
_refine_diff_density_min         -0.381
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 6404 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.487(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2524
_refine_ls_number_reflns         30440
_refine_ls_number_restraints     518
_refine_ls_restrained_S_all      0.999
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0434
_refine_ls_shift/su_max          0.024
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0293P)^2^+10.9630P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0900
_refine_ls_wR_factor_ref         0.0954
_reflns_Friedel_coverage         0.420
_reflns_Friedel_fraction_full    0.437
_reflns_Friedel_fraction_max     0.405
_reflns_number_gt                26513
_reflns_number_total             30440
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05666g2.cif
_cod_data_source_block           compound_2
_cod_database_code               1576721
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C100 H100 Cu3 P4'
_chemical_oxdiff_usercomment     ' '
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C305-C304 \\sim C1A-C1B
 with sigma of 0.02
 C305-C300 \\sim C1A-C202
 with sigma of 0.02
 C301-C300 \\sim C1E-C202
 with sigma of 0.02
 C301-C302 \\sim C1E-C1D
 with sigma of 0.02
 C304-C303 \\sim C1B-C1C
 with sigma of 0.02
 C302-C303 \\sim C1D-C1C
 with sigma of 0.02
 C305-C301 \\sim C1A-C1E
 with sigma of 0.04
 C305-C303 \\sim C1A-C1C
 with sigma of 0.04
 C301-C303 \\sim C1E-C1C
 with sigma of 0.04
 C304-C300 \\sim C1B-C202
 with sigma of 0.04
 C304-C302 \\sim C1B-C1D
 with sigma of 0.04
 C300-C302 \\sim C202-C1D
 with sigma of 0.04
 C803-C802 \\sim C1I-C1J
 with sigma of 0.02
 C803-C804 \\sim C1I-C1H
 with sigma of 0.02
 C802-C801 \\sim C1J-C152
 with sigma of 0.02
 C805-C800 \\sim C1G-C1F
 with sigma of 0.02
 C805-C804 \\sim C1G-C1H
 with sigma of 0.02
 C800-C801 \\sim C1F-C152
 with sigma of 0.02
 C803-C805 \\sim C1I-C1G
 with sigma of 0.04
 C803-C801 \\sim C1I-C152
 with sigma of 0.04
 C802-C800 \\sim C1J-C1F
 with sigma of 0.04
 C802-C804 \\sim C1J-C1H
 with sigma of 0.04
 C805-C801 \\sim C1G-C152
 with sigma of 0.04
 C800-C804 \\sim C1F-C1H
 with sigma of 0.04
 C402-C401 \\sim C1K-C203
 with sigma of 0.02
 C402-C403 \\sim C1K-C1L
 with sigma of 0.02
 C405-C404 \\sim C1M-C1N
 with sigma of 0.02
 C405-C403 \\sim C1M-C1L
 with sigma of 0.02
 C404-C400 \\sim C1N-C1O
 with sigma of 0.02
 C401-C400 \\sim C203-C1O
 with sigma of 0.02
 C402-C405 \\sim C1K-C1M
 with sigma of 0.04
 C402-C400 \\sim C1K-C1O
 with sigma of 0.04
 C405-C400 \\sim C1M-C1O
 with sigma of 0.04
 C404-C401 \\sim C1N-C203
 with sigma of 0.04
 C404-C403 \\sim C1N-C1L
 with sigma of 0.04
 C401-C403 \\sim C203-C1L
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C1A \\sim C305 \\sim C1B \\sim C304 \\sim C303 \\sim C1C \\sim C302 \\sim C1D
\\sim C1E \\sim C301 \\sim C202 \\sim C300: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.7A
C1F \\sim C800 \\sim C1G \\sim C805 \\sim C1H \\sim C804 \\sim C1I \\sim C803
\\sim C1J \\sim C802 \\sim C152 \\sim C801: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.7A
C401 \\sim C203 \\sim C400 \\sim C1O \\sim C1N \\sim C404 \\sim C405 \\sim C1M
\\sim C403 \\sim C1L \\sim C402 \\sim C1K: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.7A
4. Others
 Sof(C1E)=Sof(H1E)=Sof(C1A)=Sof(H1A)=Sof(C202)=Sof(H202)=Sof(C1D)=Sof(H1D)=
 Sof(C1C)=Sof(H1C)=Sof(C1B)=Sof(H1B)=1-FVAR(1)
 Sof(C305)=Sof(H305)=Sof(C300)=Sof(H300)=Sof(C302)=Sof(H302)=Sof(C303)=
 Sof(H303)=Sof(C304)=Sof(H304)=Sof(C301)=Sof(H301)=FVAR(1)
 Sof(C152)=Sof(H152)=Sof(C1F)=Sof(H1F)=Sof(C1G)=Sof(H1G)=Sof(C1H)=Sof(H1H)=
 Sof(C1I)=Sof(H1I)=Sof(C1J)=Sof(H1J)=1-FVAR(2)
 Sof(C803)=Sof(H803)=Sof(C802)=Sof(H802)=Sof(C805)=Sof(H805)=Sof(C800)=
 Sof(H800)=Sof(C804)=Sof(H804)=Sof(C801)=Sof(H801)=FVAR(2)
 Sof(C203)=Sof(H203)=Sof(C1K)=Sof(H1K)=Sof(C1L)=Sof(H1L)=Sof(C1M)=Sof(H1M)=
 Sof(C1N)=Sof(H1N)=Sof(C1O)=Sof(H1O)=1-FVAR(3)
 Sof(C402)=Sof(H402)=Sof(C405)=Sof(H405)=Sof(C404)=Sof(H404)=Sof(C401)=
 Sof(H401)=Sof(C403)=Sof(H403)=Sof(C400)=Sof(H400)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C151(H151), C51(H51), C101(H101), C1(H1)
5.b Secondary CH2 refined with riding coordinates:
 C177(H17A,H17B), C76(H76A,H76B), C126(H12A,H12B), C26(H26A,H26B)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C121(H121), C150(H150), C53(H53), C71(H71), C98(H98), C40(H40),
 C193(H193), C28(H28), C123(H123), C192(H192), C65(H65), C134(H134), C92(H92),
 C166(H166), C162(H162), C10(H10), C109(H109), C66(H66), C103(H103), C32(H32),
 C42(H42), C189(H189), C34(H34), C25(H25), C125(H125), C18(H18), C164(H164),
 C119(H119), C144(H144), C82(H82), C15(H15), C54(H54), C11(H11), C84(H84),
 C170(H170), C9(H9), C99(H99), C29(H29), C115(H115), C138(H138), C183(H183),
 C46(H46), C91(H91), C88(H88), C13(H13), C167(H167), C4(H4), C96(H96),
 C110(H110), C90(H90), C141(H141), C172(H172), C63(H63), C197(H197), C21(H21),
 C74(H74), C160(H160), C148(H148), C68(H68), C149(H149), C75(H75), C116(H116),
 C142(H142), C59(H59), C191(H191), C55(H55), C35(H35), C803(H803), C47(H47),
 C73(H73), C137(H137), C173(H173), C24(H24), C113(H113), C87(H87), C140(H140),
 C153(H153), C128(H128), C168(H168), C16(H16), C132(H132), C86(H86), C154(H154),
  C19(H19), C44(H44), C107(H107), C97(H97), C112(H112), C41(H41), C188(H188),
 C163(H163), C201(H201), C12(H12), C129(H129), C72(H72), C182(H182), C194(H194),
  C104(H104), C57(H57), C802(H802), C106(H106), C701(H701), C143(H143),
 C124(H124), C48(H48), C43(H43), C7(H7), C147(H147), C17(H17), C50(H50),
 C174(H174), C81(H81), C157(H157), C6(H6), C155(H155), C62(H62), C180(H180),
 C31(H31), C94(H94), C161(H161), C61(H61), C702(H702), C100(H100), C179(H179),
 C117(H117), C805(H805), C60(H60), C36(H36), C175(H175), C111(H111), C118(H118),
  C604(H604), C198(H198), C85(H85), C704(H704), C80(H80), C122(H122), C5(H5),
 C800(H800), C79(H79), C56(H56), C23(H23), C169(H169), C105(H105), C185(H185),
 C22(H22), C131(H131), C603(H603), C67(H67), C135(H135), C93(H93), C78(H78),
 C156(H156), C69(H69), C601(H601), C402(H402), C602(H602), C186(H186),
 C504(H504), C195(H195), C176(H176), C146(H146), C49(H49), C804(H804), C30(H30),
  C505(H505), C405(H405), C705(H705), C703(H703), C187(H187), C37(H37),
 C305(H305), C300(H300), C1E(H1E), C302(H302), C303(H303), C304(H304),
 C130(H130), C700(H700), C404(H404), C401(H401), C136(H136), C181(H181),
 C503(H503), C38(H38), C301(H301), C403(H403), C501(H501), C502(H502),
 C605(H605), C600(H600), C801(H801), C500(H500), C400(H400), C200(H200),
 C199(H199), C1A(H1A), C202(H202), C1D(H1D), C1C(H1C), C1B(H1B), C152(H152),
 C1F(H1F), C1G(H1G), C1H(H1H), C1I(H1I), C1J(H1J), C203(H203), C1K(H1K),
 C1L(H1L), C1M(H1M), C1N(H1N), C1O(H1O)
5.d Fitted hexagon refined as free rotating group:
 C305(C300,C1E,C302,C303,C304), C152(C1F,C1G,C1H,C1I,C1J)

Disorder Modelling Details: Three molecules of benzene in the asymmetric 
unit were positionally disordered over two positions. As a result, they 
were each split into two parts and refined with an occupancy ratio of 
0.7:0.3 (C(300)-C(305), C(202), C(1A)-C(1E)), 0.68:0.32 (C(400)-C(405), 
C(203), C(1K)-C(1O)) and 0.62:0.38 (C(800)-C(805), C(152), C(1F)-C(1J)). 
The thermal parameters of the carbon atoms of each split benzene were 
restrained to be similar to one another through the use of the SIMU command, 
and two of the benzenes were constrained with AFIX 66 ((C(300)-C(305), C(202), 
C(1A)-C(1E) and  C(800)-C(805), C(152), C(1F)-C(1J)). Approximately 1 molecule
of benzene was removed from the asymmetric unit using the Solvent Mask.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              38976
_shelx_fab_checksum              7530
_ins_header
;
TITL 012bec21-bec in P2/n 
REM P2/n (#13 in standard setting)
CELL 1.54184  15.881597  14.803620  44.255144  90.0000  97.0578  90.0000
ZERR    4.00   0.000143   0.000131   0.000348   0.0000   0.0008   0.0000
LATT  1
SYMM -x+1/2, y,-z+1/2 
SFAC C H P Cu
UNIT 400.00 400.00 16.00 12.00
REM  CrysAlisPro recorded range (K): Min=149.9; max=150.1; aver:150.0
TEMP -123
TREF
HKLF 4
END
;
_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 1.113
_oxdiff_exptl_absorpt_empirical_full_min 0.914