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_1576717
_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         'C76 H42 Cu2 F20 O4 P4 Zn2, 2(C6 H6)'
_chemical_formula_sum            'C88 H54 Cu2 F20 O4 P4 Zn2'
_chemical_formula_weight         1937.01
_chemical_name_common            021bec22
_chemical_name_systematic        '[Cu2(dppm'')2{Zn(C6F5)2}2]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-06-12 deposited with the CCDC.	2025-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                82.473(2)
_cell_angle_beta                 66.962(2)
_cell_angle_gamma                64.233(2)
_cell_formula_units_Z            1
_cell_length_a                   12.6129(3)
_cell_length_b                   13.1510(4)
_cell_length_c                   14.4377(4)
_cell_measurement_reflns_used    16415
_cell_measurement_temperature    150.01(17)
_cell_measurement_theta_max      76.1570
_cell_measurement_theta_min      3.6990
_cell_volume                     1982.48(11)
_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 1.5 (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_environment      N~2~
_diffrn_ambient_temperature      150.01(17)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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   -113.00 -15.00   1.00    1.00    --  -42.66 -70.00  24.00   98
  2  \w      1.00  35.00   1.00    1.00    --  -42.66  19.00  90.00   34
  3  \w      1.00  36.00   1.00    1.00    --  -42.66  19.00-180.00   35
  4  \w     -4.00  30.00   1.00    1.00    --  -42.66  19.00 -60.00   34
  5  \w    -44.00   8.00   1.00    1.00    --  -42.66  57.00-120.00   52
  6  \w     -5.00  35.00   1.00    1.00    --  -42.66  19.00 150.00   40
  7  \w     75.00 127.00   1.00    1.00    --   42.66-178.00  90.00   52
  8  \w     73.00 119.00   1.00    1.00    --   42.66-178.00-120.00   46
  9  \w     40.00  70.00   1.00    4.00    --  111.00 -45.00-120.00   30
 10  \w     47.00 111.00   1.00    4.00    --  111.00-125.00 -60.00   64
 11  \w     45.00  72.00   1.00    4.00    --  111.00 -45.00 -30.00   27
 12  \w     45.00  94.00   1.00    4.00    --  111.00-125.00  90.00   49
 13  \w     44.00 100.00   1.00    4.00    --  111.00 -95.00 -30.00   56
 14  \w    107.00 159.00   1.00    4.00    --  111.00  77.00 -90.00   52
 15  \w     49.00  74.00   1.00    4.00    --  111.00 -61.00  90.00   25
 16  \w     42.00  71.00   1.00    4.00    --  111.00 -45.00-150.00   29
 17  \w     64.00  89.00   1.00    4.00    --  111.00 -61.00-180.00   25
 18  \w     40.00  66.00   1.00    4.00    --  111.00 -45.00 -60.00   26
 19  \w     88.00 171.00   1.00    4.00    --  111.00  45.00 -30.00   83
 20  \w     63.00  88.00   1.00    4.00    --  111.00 -61.00 -60.00   25
 21  \w     45.00  71.00   1.00    4.00    --  111.00-125.00 150.00   26
 22  \w     86.00 112.00   1.00    4.00    --  111.00-125.00 150.00   26
 23  \w     98.00 149.00   1.00    4.00    --  111.00  30.00  30.00   51
 24  \w     58.00  85.00   1.00    4.00    --  111.00 -61.00  30.00   27
 25  \w    106.00 139.00   1.00    4.00    --  111.00 125.00 -90.00   33
 26  \w    143.00 178.00   1.00    4.00    --  111.00 125.00 -90.00   35
 27  \w     99.00 132.00   1.00    4.00    --  111.00 125.00  60.00   33
 28  \w     42.00  75.00   1.00    4.00    --  111.00-125.00 120.00   33
 29  \w     85.00 112.00   1.00    4.00    --  111.00-125.00 120.00   27
 30  \w    117.00 143.00   1.00    4.00    --  111.00  30.00-150.00   26
 31  \w     73.00 112.00   1.00    4.00    --  111.00-125.00  60.00   39
 32  \w    148.00 178.00   1.00    4.00    --  111.00  30.00-150.00   30
 33  \w     40.00  67.00   1.00    4.00    --  111.00 -45.00 150.00   27
 34  \w     65.00  90.00   1.00    4.00    --  111.00 -61.00 150.00   25
 35  \w     39.00 112.00   1.00    4.00    --  111.00-125.00-150.00   73
 36  \w     90.00 175.00   1.00    4.00    --  111.00  45.00-120.00   85
 37  \w     42.00  68.00   1.00    4.00    --  111.00 -45.00  60.00   26
 38  \w     86.00 112.00   1.00    4.00    --  111.00-125.00 -90.00   26
 39  \w     38.00 108.00   1.00    4.00    --  111.00-104.00 -55.10   70
 40  \w      3.00   4.00   1.00    1.00    --   38.00  89.00-130.76    1
;
_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      -0.0617748000
_diffrn_orient_matrix_UB_12      0.1299632000
_diffrn_orient_matrix_UB_13      -0.0011188000
_diffrn_orient_matrix_UB_21      0.0298776000
_diffrn_orient_matrix_UB_22      0.0080499000
_diffrn_orient_matrix_UB_23      0.0918263000
_diffrn_orient_matrix_UB_31      0.1291808000
_diffrn_orient_matrix_UB_32      -0.0016902000
_diffrn_orient_matrix_UB_33      -0.0710037000
_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  0.0226
_diffrn_reflns_av_unetI/netI     0.0224
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20261
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.175
_diffrn_reflns_theta_min         3.330
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.934
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87306
_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            colourless
_exptl_crystal_density_diffrn    1.622
_exptl_crystal_description       block
_exptl_crystal_F_000             972
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Benzene (slow evaporation)'
_exptl_crystal_size_max          0.272
_exptl_crystal_size_mid          0.248
_exptl_crystal_size_min          0.166
_refine_diff_density_max         0.321
_refine_diff_density_min         -0.572
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.930
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     541
_refine_ls_number_reflns         8192
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.930
_refine_ls_R_factor_all          0.0288
_refine_ls_R_factor_gt           0.0275
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1015
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7829
_reflns_number_total             8192
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05666g2.cif
_cod_data_source_block           compound5
_cod_original_cell_volume        1982.48(10)
_cod_database_code               1576717
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C25 H25 Cu2 P4 O2 Zn2'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C14(H14), C26(H26), C20(H20), C4(H4), C22(H22), C11(H11), C19(H19),
 C25(H25), C24(H24), C23(H23), C16(H16), C18(H18), C13(H13), C12(H12), C17(H17),
  C8(H8), C5(H5), C6(H6), C104(H104), C105(H105), C100(H100), C7(H7),
 C103(H103), C101(H101), C102(H102)
;
_shelx_res_checksum              91912
_ins_header
;
TITL 021bec22 in P1 
REM P1 (#1 in standard setting)
CELL 1.54184  12.612878  13.151028  14.437672  82.4733  66.9623  64.2326
ZERR    2.00   0.000302   0.000354   0.000428   0.0024   0.0025   0.0025
LATT -1
SFAC C H O P Cu Zn
UNIT 50.00 50.00 4.00 8.00 4.00 4.00
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 1.193
_oxdiff_exptl_absorpt_empirical_full_min 0.878