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_1576719
_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, 2(C6 H6)'
_chemical_formula_sum            'C86 H54 Cu2 F20 P4 Zn2'
_chemical_formula_weight         1848.99
_chemical_name_common            019bec22
_chemical_name_systematic        cis-[Cu2(dppm')2{Zn(C6F5)2}2]
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-01-26
_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                90
_cell_angle_beta                 90.6530(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.7872(2)
_cell_length_b                   15.1283(2)
_cell_length_c                   32.1498(4)
_cell_measurement_reflns_used    28006
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.4430
_cell_measurement_theta_min      3.8880
_cell_volume                     8164.29(18)
_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      150.00(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 0.995
_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  33.00   1.00    2.50    --  -41.40  19.00-150.00   30
  2  \w      0.00  34.00   1.00    2.50    --  -41.40  19.00-180.00   34
  3  \w      6.00  32.00   1.00    2.50    --  -41.40  19.00 -60.00   26
  4  \w     -5.00  36.00   1.00    2.50    --  -41.40  19.00 -30.00   41
  5  \w    -83.00 -13.00   1.00    2.50    --  -41.40 125.00  60.00   70
  6  \w     45.00  90.00   1.00    2.50    --   41.40-125.00 -30.00   45
  7  \w     56.00  93.00   1.00   12.50    --  111.00 -61.00   0.00   37
  8  \w     43.00  72.00   1.00   12.50    --  111.00 -45.00  30.00   29
  9  \w     75.00 111.00   1.00   12.50    --  111.00 -77.00 150.00   36
 10  \w     33.00  64.00   1.00   12.50    --  111.00 -94.00   0.00   31
 11  \w     74.00 106.00   1.00   12.50    --  111.00 -94.00   0.00   32
 12  \w     45.00  72.00   1.00   12.50    --  111.00 -45.00-180.00   27
 13  \w     42.00  69.00   1.00   12.50    --  111.00 -45.00 -90.00   27
 14  \w     63.00  88.00   1.00   12.50    --  111.00 -61.00 -90.00   25
 15  \w    107.00 176.00   1.00   12.50    --  111.00  77.00  30.00   69
 16  \w     44.00  74.00   1.00   12.50    --  111.00 -61.00 150.00   30
 17  \w    108.00 172.00   1.00   12.50    --  111.00  77.00  60.00   64
 18  \w     42.00  69.00   1.00   12.50    --  111.00 -45.00 -30.00   27
 19  \w     44.00  92.00   1.00   12.50    --  111.00 -61.00-180.00   48
 20  \w     70.00 124.00   1.00   12.50    --  111.00 -77.00  60.00   54
 21  \w     76.00 103.00   1.00   12.50    --  111.00-125.00  30.00   27
 22  \w    124.00 157.00   1.00   12.50    --  111.00  77.00-120.00   33
 23  \w     46.00  72.00   1.00   12.50    --  111.00 -45.00-150.00   26
 24  \w     37.00  63.00   1.00   12.50    --  111.00 -77.00 150.00   26
 25  \w     82.00 107.00   1.00   12.50    --  111.00-103.00-140.00   25
 26  \w     -5.00  20.00   1.00    2.50    --  -41.40  19.00 -60.00   25
 27  \w     -5.00  35.00   1.00    2.50    --  -41.40  19.00  60.00   40
 28  \w     -4.00  32.00   1.00    2.50    --  -41.40  19.00 -90.00   36
 29  \w     28.00  54.00   1.00    2.50    --   41.40-125.00-120.00   26
 30  \w     34.00  60.00   1.00    2.50    --   41.40-125.00  90.00   26
 31  \w     13.00  48.00   1.00    2.50    --   41.40 -99.00 -30.00   35
 32  \w     59.00 107.00   1.00   12.50    --  111.00-101.00 117.30   48
 33  \w     93.00 125.00   1.00   12.50    --  111.00-141.00 106.50   32
 34  \w     82.00 107.00   1.00   12.50    --  111.00 -94.00 -60.00   25
 35  \w     39.00  76.00   1.00   12.50    --  111.00 -94.00 -60.00   37
 36  \w    102.00 127.00   1.00   12.50    --  111.00-144.00  45.93   25
 37  \w     91.00 123.00   1.00   12.50    --  111.00  30.00 -90.00   32
 38  \w    151.00 176.00   1.00   12.50    --  111.00  30.00 -90.00   25
 39  \w     98.00 142.00   1.00   12.50    --  111.00  45.00-180.00   44
 40  \w     73.00  98.00   1.00   12.50    --  111.00-125.00 120.00   25
 41  \w    102.00 143.00   1.00   12.50    --  111.00  30.00 -30.00   41
 42  \w     41.00  71.00   1.00   12.50    --  111.00 -45.00   0.00   30
 43  \w     82.00 107.00   1.00   12.50    --  111.00 -94.00 120.00   25
 44  \w     37.00  74.00   1.00   12.50    --  111.00 -94.00 120.00   37
 45  \w     67.00 108.00   1.00   12.50    --  111.00-105.00 -78.34   41
 46  \w     44.00  71.00   1.00   12.50    --  111.00 -94.00 150.00   27
 47  \w     75.00 101.00   1.00   12.50    --  111.00 -94.00 150.00   26
 48  \w     97.00 167.00   1.00   12.50    --  111.00  30.00  30.00   70
 49  \w    108.00 133.00   1.00   12.50    --  111.00  77.00-180.00   25
 50  \w     88.00 172.00   1.00   12.50    --  111.00  30.00 150.00   84
;
_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      -0.0392560000
_diffrn_orient_matrix_UB_12      0.0920103000
_diffrn_orient_matrix_UB_13      0.0007992000
_diffrn_orient_matrix_UB_21      0.0212538000
_diffrn_orient_matrix_UB_22      0.0135759000
_diffrn_orient_matrix_UB_23      -0.0460447000
_diffrn_orient_matrix_UB_31      -0.0802075000
_diffrn_orient_matrix_UB_32      -0.0414290000
_diffrn_orient_matrix_UB_33      -0.0132521000
_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  0.0271
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            45096
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.338
_diffrn_reflns_theta_min         3.934
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.781
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76883
_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    1.504
_exptl_crystal_description       block
_exptl_crystal_F_000             3712
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Benzene (slow evaporation)'
_exptl_crystal_size_max          0.254
_exptl_crystal_size_mid          0.161
_exptl_crystal_size_min          0.085
_exptl_transmission_factor_max   1.00000
_exptl_transmission_factor_min   0.76883
_refine_diff_density_max         0.408
_refine_diff_density_min         -0.257
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.884
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     569
_refine_ls_number_reflns         8528
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      0.889
_refine_ls_R_factor_all          0.0294
_refine_ls_R_factor_gt           0.0260
_refine_ls_shift/su_max          0.001
_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          0.0947
_refine_ls_wR_factor_ref         0.1007
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7769
_reflns_number_total             8528
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05666g2.cif
_cod_data_source_block           compound_cis4
_cod_database_code               1576719
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C60 H60 Cu3 F10 P6 Zn3'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C107-C108 \\sim C101-C102
 with sigma of 0.02
 C107-C106 \\sim C101-C100
 with sigma of 0.02
 C111-C109 \\sim C105-C103
 with sigma of 0.04
 C110-C106 \\sim C104-C100
 with sigma of 0.04
 C111-C110 \\sim C105-C104
 with sigma of 0.02
 C111-C106 \\sim C105-C100
 with sigma of 0.02
 C108-C106 \\sim C102-C100
 with sigma of 0.04
 C108-C109 \\sim C102-C103
 with sigma of 0.02
 C110-C109 \\sim C104-C103
 with sigma of 0.02
 C108-C110 \\sim C102-C104
 with sigma of 0.04
 C107-C111 \\sim C101-C105
 with sigma of 0.04
 C107-C109 \\sim C101-C103
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C108 \\sim C102 \\sim C107 \\sim C101 \\sim C106 \\sim C100 \\sim C105 \\sim
C111 \\sim C104 \\sim C110 \\sim C103 \\sim C109: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 1.7A
4. Others
 Sof(C103)=Sof(H103)=Sof(C102)=Sof(H102)=Sof(C101)=Sof(H101)=Sof(C100)=
 Sof(H100)=Sof(C105)=Sof(H105)=Sof(C104)=Sof(H104)=1-FVAR(1)
 Sof(C107)=Sof(H107)=Sof(C111)=Sof(H111)=Sof(C108)=Sof(H108)=Sof(C110)=
 Sof(H110)=Sof(C109)=Sof(H109)=Sof(C106)=Sof(H106)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1(H1)
5.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C21(H21), C3(H3), C22(H22), C7(H7), C9(H9), C13(H13), C23(H23),
 C15(H15), C5(H5), C4(H4), C24(H24), C11(H11), C19(H19), C6(H6), C10(H10),
 C12(H12), C16(H16), C17(H17), C18(H18), C107(H107), C111(H111), C108(H108),
 C110(H110), C109(H109), C106(H106), C103(H103), C102(H102), C101(H101),
 C100(H100), C105(H105), C104(H104)

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 0.73:0.27. The thermal 
parameters of the carbon atoms were restrained to be similar to one another 
through the use of the SIMU command, and the C-C bond lengths were restrained 
to be equal using the SADI command.
;
_shelx_res_checksum              55746
_ins_header
;
TITL 019bec22 in I2/a 
REM I2/a (#15 in standard setting)
CELL 1.54184  16.787226  15.128322  32.149785  90.0000  90.6528  90.0000
ZERR    4.00   0.000183   0.000180   0.000372   0.0000   0.0010   0.0000
LATT  2
SYMM -x+1/2, y,-z 
SFAC C H F P Cu Zn
UNIT 240.00 240.00 40.00 24.00 12.00 12.00
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 1.323
_oxdiff_exptl_absorpt_empirical_full_min 0.828