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_1576720
_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         'C77 H68 Cu3 O4 P6, C6 H6'
_chemical_formula_sum            'C83 H74 Cu3 O4 P6'
_chemical_formula_weight         1511.86
_chemical_name_common            027bec23
_chemical_name_systematic        '[Cu3(k1-O2CH)(k2:u2-O2CH)(dppm)3]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-09
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-12 deposited with the CCDC.	2025-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.9630(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.8464(2)
_cell_length_b                   41.8005(6)
_cell_length_c                   17.7632(2)
_cell_measurement_reflns_used    24120
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      76.4150
_cell_measurement_theta_min      3.9980
_cell_volume                     8023.4(2)
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_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     -9.00  31.00   1.00    1.50    --  -41.40  37.00 150.00   40
  2  \w    -12.00  16.00   1.00    1.50    --  -41.40  37.00-120.00   28
  3  \w      1.00  31.00   1.00    1.50    --  -41.40  19.00 120.00   30
  4  \w    -20.00  29.00   1.00    1.50    --  -41.40  37.00-150.00   49
  5  \w    -21.00  24.00   1.00    1.50    --  -41.40  37.00 -90.00   45
  6  \w   -107.00 -82.00   1.00    1.50    --  -41.40-146.00 -34.00   25
  7  \w     33.00  93.00   1.00    1.50    --   41.40-125.00-150.00   60
  8  \w     89.00 153.00   1.00    6.00    --  111.00  45.00 -60.00   64
  9  \w    133.00 165.00   1.00    6.00    --  111.00  77.00 150.00   32
 10  \w     83.00 109.00   1.00    6.00    --  111.00  61.00  60.00   26
 11  \w     87.00 112.00   1.00    6.00    --  111.00-125.00 120.00   25
 12  \w     79.00 112.00   1.00    6.00    --  111.00-125.00 -90.00   33
 13  \w     45.00  76.00   1.00    6.00    --  111.00-125.00 120.00   31
 14  \w    110.00 142.00   1.00    6.00    --  111.00  77.00  30.00   32
 15  \w     41.00  91.00   1.00    6.00    --  111.00 -61.00 -30.00   50
 16  \w     59.00  87.00   1.00    6.00    --  111.00 -61.00  60.00   28
 17  \w     54.00 100.00   1.00    6.00    --  111.00-125.00   0.00   46
 18  \w    112.00 174.00   1.00    6.00    --  111.00  77.00 120.00   62
 19  \w     41.00  93.00   1.00    6.00    --  111.00 -61.00-150.00   52
 20  \w    114.00 161.00   1.00    6.00    --  111.00  61.00  60.00   47
 21  \w     48.00 124.00   1.00    6.00    --  111.00-140.00-102.39   76
 22  \w     71.00  96.00   1.00    6.00    --  111.00-125.00-150.00   25
 23  \w     66.00 109.00   1.00    6.00    --  111.00-111.00 160.83   43
 24  \w    -84.00  -8.00   1.00    1.50    --  -41.40 125.00 -60.00   76
 25  \w    -33.00  -8.00   1.00    1.50    --  -41.40  57.00 -90.00   25
 26  \w      4.00  29.00   1.00    1.50    --  -41.40  57.00 -90.00   25
 27  \w     -4.00  37.00   1.00    1.50    --  -41.40  19.00 -60.00   41
 28  \w      4.00  30.00   1.00    1.50    --  -41.40  19.00-180.00   26
 29  \w      7.00  36.00   1.00    1.50    --  -41.40  19.00  60.00   29
 30  \w     40.00  66.00   1.00    1.50    --   41.40-125.00 120.00   26
 31  \w     40.00  65.00   1.00    6.00    --  111.00 -77.00  30.00   25
 32  \w     58.00  90.00   1.00    6.00    --  111.00 -61.00 120.00   32
 33  \w    103.00 161.00   1.00    6.00    --  111.00  45.00-120.00   58
;
_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      -0.0184196000
_diffrn_orient_matrix_UB_12      -0.0363166000
_diffrn_orient_matrix_UB_13      0.0087040000
_diffrn_orient_matrix_UB_21      -0.1368347000
_diffrn_orient_matrix_UB_22      0.0056437000
_diffrn_orient_matrix_UB_23      0.0131848000
_diffrn_orient_matrix_UB_31      -0.0356045000
_diffrn_orient_matrix_UB_32      -0.0028182000
_diffrn_orient_matrix_UB_33      -0.0855952000
_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  0.0438
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -52
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            58636
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.681
_diffrn_reflns_theta_min         4.038
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.414
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90447
_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    1.252
_exptl_crystal_description       block
_exptl_crystal_F_000             3124
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: benzene/hexanes (vapour diffusion)'
_exptl_crystal_size_max          0.308
_exptl_crystal_size_mid          0.229
_exptl_crystal_size_min          0.073
_exptl_transmission_factor_max   1.00000
_exptl_transmission_factor_min   0.90447
_refine_diff_density_max         1.060
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     896
_refine_ls_number_reflns         16574
_refine_ls_number_restraints     186
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0562
_refine_ls_R_factor_gt           0.0480
_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          0.1446
_refine_ls_wR_factor_ref         0.1517
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14076
_reflns_number_total             16574
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05666g2.cif
_cod_data_source_block           compound_3
_cod_database_code               1576720
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H50 P6 O4'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C102-C103 \\sim C202-C203
 with sigma of 0.02
 C102-C101 \\sim C202-C201
 with sigma of 0.02
 C104-C103 \\sim C204-C203
 with sigma of 0.02
 C104-C105 \\sim C204-C205
 with sigma of 0.02
 C105-C100 \\sim C205-C200
 with sigma of 0.02
 C101-C100 \\sim C201-C200
 with sigma of 0.02
 C102-C104 \\sim C202-C204
 with sigma of 0.04
 C102-C100 \\sim C202-C200
 with sigma of 0.04
 C104-C100 \\sim C204-C200
 with sigma of 0.04
 C103-C105 \\sim C203-C205
 with sigma of 0.04
 C103-C101 \\sim C203-C201
 with sigma of 0.04
 C105-C101 \\sim C205-C201
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C203 \\sim C103 \\sim C204 \\sim C104 \\sim C205 \\sim C105 \\sim C200 \\sim
C100 \\sim C101 \\sim C201 \\sim C102 \\sim C202: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 1.7A
4. Others
 Sof(C204)=Sof(H204)=Sof(C205)=Sof(H205)=Sof(C200)=Sof(H200)=Sof(C201)=
 Sof(H201)=Sof(C202)=Sof(H202)=Sof(C203)=Sof(H203)=1-FVAR(1)
 Sof(C103)=Sof(H103)=Sof(C102)=Sof(H102)=Sof(C101)=Sof(H101)=Sof(C100)=
 Sof(H100)=Sof(C105)=Sof(H105)=Sof(C104)=Sof(H104)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C3(H3A,H3B), C28(H28A,H28B)
5.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C17(H17), C23(H23), C21(H21), C2(H2), C61(H61), C19(H19), C20(H20),
 C18(H18), C73(H73), C24(H24), C26(H26), C65(H65), C25(H25), C77(H77), C59(H59),
  C46(H46), C15(H15), C71(H71), C62(H62), C11(H11), C42(H42), C63(H63),
 C64(H64), C9(H9), C67(H67), C55(H55), C58(H58), C48(H48), C52(H52), C75(H75),
 C7(H7), C76(H76), C36(H36), C74(H74), C8(H8), C1(H1), C45(H45), C40(H40),
 C57(H57), C5(H5), C14(H14), C34(H34), C30(H30), C43(H43), C13(H13), C70(H70),
 C37(H37), C12(H12), C68(H68), C56(H56), C6(H6), C44(H44), C69(H69), C38(H38),
 C39(H39), C49(H49), C31(H31), C33(H33), C50(H50), C51(H51), C32(H32),
 C103(H103), C102(H102), C101(H101), C100(H100), C105(H105), C104(H104),
 C204(H204), C205(H205), C200(H200), C201(H201), C202(H202), C203(H203)
5.c Fitted hexagon refined as free rotating group:
 C103(C102,C101,C100,C105,C104), C204(C205,C200,C201,C202,C203)

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 0.52:0.48. The thermal 
parameters of the carbon atoms were restrained to be similar to one another 
through the use of the SIMU command. Approximately two molecules of benzene
were removed from the asymmetric unit using the "solvent mask" feature of
Olex2. The u3-hydrido ligand was not located in the difference map.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              64568
_shelx_fab_checksum              53862
_ins_header
;
TITL 027bec23 in P2(1)/c 
REM P2(1)/c (#14 in standard setting)
CELL 1.54184  10.846396  41.800498  17.763235  90.0000  94.9627  90.0000
ZERR    4.00   0.000164   0.000588   0.000229   0.0000   0.0014   0.0000
LATT  1
SYMM -x, y+1/2,-z+1/2 
SFAC C H O P
UNIT 200.00 200.00 16.00 24.00
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 1.303
_oxdiff_exptl_absorpt_empirical_full_min 0.855