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_1576718
_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         'C74 H42 Cu2 F20 P4 Zn2, 3(C6 H6)'
_chemical_formula_sum            'C92 H60 Cu2 F20 P4 Zn2'
_chemical_formula_weight         1927.10
_chemical_name_common            026bec23
_chemical_name_systematic        trans-[Cu2(dppm')2{Zn(C6F5)2}2]
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-07
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-06-12 deposited with the CCDC.	2025-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.4260(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.94460(10)
_cell_length_b                   18.93720(10)
_cell_length_c                   15.52070(10)
_cell_measurement_reflns_used    65955
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.3880
_cell_measurement_theta_min      3.8260
_cell_volume                     4043.24(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_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(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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      0.00  25.00   1.00    1.00    --  -41.52  19.00-150.00   25
  2  \w     -3.00  35.00   1.00    1.00    --  -41.52  19.00 -30.00   38
  3  \w     -3.00  36.00   1.00    1.00    --  -41.52  19.00   0.00   39
  4  \w     -2.00  26.00   1.00    1.00    --  -41.52  19.00-120.00   28
  5  \w    -17.00  31.00   1.00    1.00    --  -41.52  37.00 -90.00   48
  6  \w      3.00  35.00   1.00    1.00    --  -41.52  19.00 120.00   32
  7  \w     46.00  83.00   1.00    1.00    --   41.52-125.00 -60.00   37
  8  \w     27.00  53.00   1.00    1.00    --   41.52-125.00-180.00   26
  9  \w     42.00  67.00   1.00    4.00    --  111.00 -45.00 -30.00   25
 10  \w     51.00 105.00   1.00    4.00    --  111.00-111.00 -30.00   54
 11  \w     66.00  92.00   1.00    4.00    --  111.00 -61.00 -60.00   26
 12  \w     43.00  71.00   1.00    4.00    --  111.00 -45.00 -60.00   28
 13  \w     44.00  72.00   1.00    4.00    --  111.00 -45.00  90.00   28
 14  \w     61.00 108.00   1.00    4.00    --  111.00-111.00  90.00   47
 15  \w    114.00 178.00   1.00    4.00    --  111.00 111.00-150.00   64
 16  \w     41.00  67.00   1.00    4.00    --  111.00 -45.00-120.00   26
 17  \w     40.00  65.00   1.00    4.00    --  111.00 -45.00-150.00   25
 18  \w     90.00 131.00   1.00    4.00    --  111.00  30.00   0.00   41
 19  \w     92.00 173.00   1.00    4.00    --  111.00  30.00-150.00   81
 20  \w     45.00  71.00   1.00    4.00    --  111.00 -45.00  60.00   26
 21  \w     43.00  84.00   1.00    4.00    --  111.00 -61.00-180.00   41
 22  \w     49.00  75.00   1.00    4.00    --  111.00 -61.00-120.00   26
 23  \w     40.00  66.00   1.00    4.00    --  111.00 -45.00 120.00   26
 24  \w     45.00  70.00   1.00    4.00    --  111.00 -45.00   0.00   25
 25  \w    114.00 142.00   1.00    4.00    --  111.00 111.00 -90.00   28
 26  \w     74.00 101.00   1.00    4.00    --  111.00-111.00-120.00   27
 27  \w     88.00 141.00   1.00    4.00    --  111.00  15.00-180.00   53
 28  \w    -29.00  15.00   1.00    1.00    --  -41.52  45.00-143.00   44
 29  \w    -83.00 -21.00   1.00    1.00    --  -41.52 125.00  60.00   62
 30  \w     -1.00  64.00   1.00    1.00    --   41.52 -37.00 -30.00   65
 31  \w     49.00  91.00   1.00    1.00    --   41.52-125.00 -30.00   42
 32  \w     39.00  85.00   1.00    4.00    --  111.00-111.00 150.00   46
 33  \w    111.00 173.00   1.00    4.00    --  111.00  30.00 -90.00   62
 34  \w    125.00 151.00   1.00    4.00    --  111.00  45.00  90.00   26
 35  \w     43.00  68.00   1.00    4.00    --  111.00-111.00 -60.00   25
 36  \w     52.00  97.00   1.00    4.00    --  111.00-111.00  60.00   45
 37  \w     73.00 109.00   1.00    4.00    --  111.00-111.00 -60.00   36
 38  \w     89.00 122.00   1.00    4.00    --  111.00  30.00  60.00   33
 39  \w    134.00 160.00   1.00    4.00    --  111.00  30.00  60.00   26
 40  \w     81.00 107.00   1.00    4.00    --  111.00 -94.00  90.00   26
 41  \w     42.00  74.00   1.00    4.00    --  111.00 -94.00-150.00   32
 42  \w     32.00  71.00   1.00    4.00    --  111.00 -94.00 -30.00   39
 43  \w     58.00  91.00   1.00    4.00    --  111.00 -61.00 120.00   33
 44  \w     82.00 107.00   1.00    4.00    --  111.00 -94.00-150.00   25
 45  \w     41.00  67.00   1.00    4.00    --  111.00 -77.00   0.00   26
 46  \w     67.00 115.00   1.00    4.00    --  111.00  15.00   0.00   48
 47  \w    138.00 166.00   1.00    4.00    --  111.00  15.00   0.00   28
 48  \w     76.00 108.00   1.00    4.00    --  111.00-111.00-180.00   32
 49  \w     67.00 106.00   1.00    4.00    --  111.00-111.00 -90.00   39
 50  \w     83.00 109.00   1.00    4.00    --  111.00-111.00  90.00   26
 51  \w    106.00 132.00   1.00    4.00    --  111.00 111.00-180.00   26
 52  \w    142.00 168.00   1.00    4.00    --  111.00 111.00-180.00   26
 53  \w     30.00  55.00   1.00    4.00    --  111.00 -94.00  90.00   25
 54  \w     43.00  72.00   1.00    4.00    --  111.00 -45.00-180.00   29
 55  \w     76.00 109.00   1.00    4.00    --  111.00-111.00   0.00   33
 56  \w     41.00  93.00   1.00    4.00    --  111.00-111.00  30.00   52
 57  \w     60.00 108.00   1.00    4.00    --  111.00-104.00-169.66   48
 58  \w    -24.00   1.00   1.00    1.00    --  -41.52  45.00-143.00   25
 59  \w     -2.00  23.00   1.00    1.00    --   34.00  91.00 -43.03   25
 60  \w     -1.00  24.00   1.00    1.00    --   34.00  88.00-124.76   25
 61  \w      2.00  27.00   1.00    1.00    --   38.00  90.00  75.07   25
 62  \w      1.00  35.00   1.00    1.00    --  -41.52  19.00 150.00   34
 63  \w      3.00  32.00   1.00    1.00    --  -41.52  19.00-180.00   29
 64  \w    -79.00 -20.00   1.00    1.00    --  -41.52 -37.00  30.00   59
 65  \w   -113.00 -19.00   1.00    1.00    --  -41.52 -37.00-180.00   94
 66  \w     13.00  38.00   1.00    1.00    --   46.00  82.00 -89.84   25
 67  \w     13.00  38.00   1.00    1.00    --   46.00  82.00 103.27   25
 68  \w     14.00  39.00   1.00    1.00    --   46.00  80.00  52.76   25
 69  \w     14.00  39.00   1.00    1.00    --   46.00  81.00 -25.72   25
 70  \w     14.00  39.00   1.00    1.00    --   46.00  80.00-170.51   25
 71  \w     28.00  55.00   1.00    1.00    --   58.00  71.00 174.88   27
 72  \w     33.00  59.00   1.00    1.00    --   62.00  69.00 -82.72   26
 73  \w     33.00  58.00   1.00    1.00    --   62.00  71.00 -41.97   25
 74  \w     33.00  60.00   1.00    1.00    --   62.00  70.00  25.75   27
 75  \w     32.00  58.00   1.00    1.00    --   62.00  70.00  95.11   26
 76  \w     36.00  62.00   1.00    1.00    --   66.00  71.00-125.51   26
 77  \w     37.00  62.00   1.00    1.00    --   66.00  71.00  43.68   25
 78  \w     36.00  62.00   1.00    1.00    --   66.00  71.00  -9.88   26
 79  \w     40.00  66.00   1.00    1.00    --   70.00  70.00 131.37   26
 80  \w    104.00 130.00   1.00    1.00    --   70.00  70.00 131.37   26
 81  \w     41.00  67.00   1.00    1.00    --   70.00  66.00 114.18   26
 82  \w    108.00 134.00   1.00    1.00    --   74.00  70.00  65.92   26
 83  \w     45.00  71.00   1.00    1.00    --   74.00  69.00 163.09   26
 84  \w     44.00  70.00   1.00    1.00    --   74.00  70.00  65.92   26
 85  \w     44.00  70.00   1.00    1.00    --   74.00  71.00-175.22   26
 86  \w     50.00  76.00   1.00    4.00    --   78.00  65.00 -95.00   26
 87  \w     53.00  81.00   1.00    4.00    --   82.00  66.00-157.99   28
 88  \w     53.00  79.00   1.00    4.00    --   82.00  69.00 -53.98   26
 89  \w     57.00  84.00   1.00    4.00    --   86.00  67.00 132.15   27
 90  \w     57.00  82.00   1.00    4.00    --   86.00  70.00 -13.72   25
 91  \w     56.00  82.00   1.00    4.00    --   86.00  70.00 110.50   26
 92  \w     57.00  84.00   1.00    4.00    --   86.00  69.00-131.23   27
 93  \w     57.00  84.00   1.00    4.00    --   86.00  68.00  29.90   27
 94  \w     57.00  83.00   1.00    4.00    --   86.00  66.00 -25.84   26
 95  \w     60.00  86.00   1.00    4.00    --   90.00  70.00 -94.98   26
 96  \w     60.00  86.00   1.00    4.00    --   90.00  71.00  66.45   26
 97  \w     62.00  89.00   1.00    4.00    --   90.00  65.00   9.90   27
 98  \w     64.00  91.00   1.00    4.00    --   94.00  70.00 140.53   27
 99  \w     70.00 114.00   1.00    4.00    --   98.00  62.00-113.81   44
100  \w     69.00  95.00   1.00    4.00    --   98.00  66.00 -31.11   26
101  \w     72.00 101.00   1.00    4.00    --   98.00  58.00-174.08   29
102  \w     80.00 111.00   1.00    4.00    --  110.00  70.00-168.45   31
103  \w    134.00 177.00   1.00    4.00    --  111.00  61.00  60.00   43
104  \w     83.00 120.00   1.00    4.00    --  111.00  61.00  60.00   37
105  \w    135.00 165.00   1.00    4.00    --  111.00  61.00  10.56   30
106  \w    134.00 170.00   1.00    4.00    --  111.00  61.00-180.00   36
107  \w     83.00 110.00   1.00    4.00    --  111.00  61.00-180.00   27
108  \w     83.00 116.00   1.00    4.00    --  111.00  61.00  10.56   33
109  \w     85.00 112.00   1.00    4.00    --  111.00  61.00 -60.00   27
110  \w    127.00 173.00   1.00    4.00    --  111.00  61.00  30.00   46
111  \w     84.00 110.00   1.00    4.00    --  111.00  61.00  30.00   26
112  \w    146.00 172.00   1.00    4.00    --  111.00  61.00 -30.00   26
113  \w    149.00 175.00   1.00    4.00    --  111.00  61.00-150.00   26
114  \w     83.00 109.00   1.00    4.00    --  111.00  61.00 -30.00   26
115  \w     84.00 119.00   1.00    4.00    --  111.00  61.00-150.00   35
116  \w     84.00 117.00   1.00    4.00    --  111.00  65.00 120.88   33
117  \w    153.00 178.00   1.00    4.00    --  111.00  65.00 120.88   25
118  \w    148.00 175.00   1.00    4.00    --  111.00  64.00 -17.36   27
119  \w     84.00 110.00   1.00    4.00    --  111.00  57.00 -62.46   26
120  \w     83.00 124.00   1.00    4.00    --  111.00  64.00 -17.36   41
121  \w    127.00 153.00   1.00    4.00    --  111.00  61.00 -90.00   26
122  \w     83.00 120.00   1.00    4.00    --  111.00  61.00 -90.00   37
123  \w    137.00 163.00   1.00    4.00    --  111.00  61.00-120.00   26
124  \w    136.00 176.00   1.00    4.00    --  111.00  59.00 -46.42   40
125  \w     85.00 111.00   1.00    4.00    --  111.00  59.00 -46.42   26
126  \w     83.00 122.00   1.00    4.00    --  111.00  61.00-120.00   39
127  \w    134.00 168.00   1.00    4.00    --  111.00  57.00 118.23   34
128  \w     85.00 111.00   1.00    4.00    --  111.00  57.00 118.23   26
129  \w    138.00 175.00   1.00    4.00    --  111.00  61.00 150.00   37
130  \w    148.00 175.00   1.00    4.00    --  111.00  56.00  82.27   27
131  \w     85.00 111.00   1.00    4.00    --  111.00  56.00  82.27   26
132  \w     84.00 120.00   1.00    4.00    --  111.00  61.00 150.00   36
133  \w     84.00 142.00   1.00    4.00    --  111.00  61.00  90.00   58
134  \w     40.00  65.00   1.00    4.00    --  111.00 -45.00 -60.00   25
135  \w    141.00 167.00   1.00    4.00    --  111.00  77.00 -60.00   26
136  \w     84.00 119.00   1.00    4.00    --  111.00  61.00   0.00   35
;
_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      0.0580430000
_diffrn_orient_matrix_UB_12      -0.0356253000
_diffrn_orient_matrix_UB_13      0.0815043000
_diffrn_orient_matrix_UB_21      -0.0727678000
_diffrn_orient_matrix_UB_22      0.0289714000
_diffrn_orient_matrix_UB_23      0.0559146000
_diffrn_orient_matrix_UB_31      -0.0622249000
_diffrn_orient_matrix_UB_32      -0.0671381000
_diffrn_orient_matrix_UB_33      -0.0190263000
_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  0.0346
_diffrn_reflns_av_unetI/netI     0.0118
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            113646
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.545
_diffrn_reflns_theta_min         3.712
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.835
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92079
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.583
_exptl_crystal_description       block
_exptl_crystal_F_000             1940
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Benzene (slow evaporation)'
_exptl_crystal_size_max          0.186
_exptl_crystal_size_mid          0.159
_exptl_crystal_size_min          0.136
_exptl_transmission_factor_max   1.00000
_exptl_transmission_factor_min   0.92079
_refine_diff_density_max         0.290
_refine_diff_density_min         -0.310
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.875
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     596
_refine_ls_number_reflns         8466
_refine_ls_number_restraints     162
_refine_ls_restrained_S_all      0.880
_refine_ls_R_factor_all          0.0260
_refine_ls_R_factor_gt           0.0233
_refine_ls_shift/su_max          0.003
_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          0.0923
_refine_ls_wR_factor_ref         0.0969
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7817
_reflns_number_total             8466
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05666g2.cif
_cod_data_source_block           compound_trans4
_cod_database_code               1576718
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H50 Cu2 F20 P4 Zn2'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C201-C200 \\sim C1A-C38
 with sigma of 0.02
 C201-C202 \\sim C1A-C1B
 with sigma of 0.02
 C200-C205 \\sim C38-C1E
 with sigma of 0.02
 C202-C203 \\sim C1B-C1C
 with sigma of 0.02
 C205-C204 \\sim C1E-C1D
 with sigma of 0.02
 C203-C204 \\sim C1C-C1D
 with sigma of 0.02
 C201-C205 \\sim C1A-C1E
 with sigma of 0.04
 C201-C203 \\sim C1A-C1C
 with sigma of 0.04
 C200-C202 \\sim C38-C1B
 with sigma of 0.04
 C200-C204 \\sim C38-C1D
 with sigma of 0.04
 C202-C204 \\sim C1B-C1D
 with sigma of 0.04
 C205-C203 \\sim C1E-C1C
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C38 \\sim C200 \\sim C1A \\sim C201 \\sim C1B \\sim C202 \\sim C1C \\sim C203
\\sim C204 \\sim C1D \\sim C205 \\sim C1E: within 1.7A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 1.7A
4. Others
 Sof(C38)=Sof(H38)=Sof(C1A)=Sof(H1A)=Sof(C1B)=Sof(H1B)=Sof(C1C)=Sof(H1C)=
 Sof(C1D)=Sof(H1D)=Sof(C1E)=Sof(H1E)=1-FVAR(1)
 Sof(C201)=Sof(H201)=Sof(C200)=Sof(H200)=Sof(C202)=Sof(H202)=Sof(C205)=
 Sof(H205)=Sof(C203)=Sof(H203)=Sof(C204)=Sof(H204)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C15(H15), C9(H9), C25(H25), C3(H3), C13(H13), C21(H21), C23(H23),
 C4(H4), C19(H19), C5(H5), C22(H22), C6(H6), C16(H16), C10(H10), C12(H12),
 C11(H11), C24(H24), C17(H17), C18(H18), C101(H101), C102(H102), C100(H100),
 C201(H201), C200(H200), C202(H202), C205(H205), C203(H203), C204(H204),
 C38(H38), C1A(H1A), C1B(H1B), C1C(H1C), C1D(H1D), C1E(H1E)

Disorder Modelling Details: A molecule of benzene in the asymmetric unit 
was positionally disordered over two positions. As a result, it was split 
into two parts and refined with an occupancy ratio of 0.66:0.34. The thermal 
parameters of the carbon atoms were restrained to be similar to one another 
through the use of the SIMU command.
;
_shelx_res_checksum              6148
_ins_header
;
TITL 026bec23 in P2(1)/n 
REM P2(1)/n (#14 in standard setting)
CELL 1.54184  13.944645  18.937155  15.520695  90.0000  99.4263  90.0000
ZERR    2.00   0.000108   0.000136   0.000118   0.0000   0.0007   0.0000
LATT  1
SYMM -x+1/2, y+1/2,-z+1/2 
SFAC C H F P Cu Zn
UNIT 100.00 100.00 40.00 8.00 4.00 4.00
REM  CrysAlisPro recorded range (K): Min=150.0; max=150.0; 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 1.100
_oxdiff_exptl_absorpt_empirical_full_min 0.932