Oxo-functionalised mesoionic NHC nickel complexes for selective electrocatalytic reduction of CO2 to formate
Bertini, Simone; Rahaman, Motiar; Dutta, Abhijit; Schollhammer, Philippe; Rudnev, Alexander V.; Gloaguen, Fredric; Broekmann, Peter; Albrecht, Martin; Green Chemistry 23 (2021) 3365–3373; doi:10.1039/D1GC00388G

data_7242640
_publ_section_title
;
 Oxo-functionalised mesoionic NHC nickel complexes for selective
 electrocatalytic reduction of CO2 to formate
;
_journal_issue                   9
_journal_name_full               'Green Chemistry'
_journal_page_first              3365
_journal_page_last               3373
_journal_paper_doi               10.1039/D1GC00388G
_journal_volume                  23
_journal_year                    2021
_chemical_formula_moiety         'C42 H64 N6 Ni O2'
_chemical_formula_sum            'C42 H64 N6 Ni O2'
_chemical_formula_weight         743.70
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-15 deposited with the CCDC.	2021-04-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.0670(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.79520(10)
_cell_length_b                   18.38130(10)
_cell_length_c                   18.97510(10)
_cell_measurement_reflns_used    25406
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      76.5150
_cell_measurement_theta_min      3.6830
_cell_volume                     4217.96(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_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    -90.00  -4.00   0.50    0.08    --  -18.75 -48.00  41.00  172
  2  \w    -23.00  51.00   0.50    0.08    --   47.95 -48.00  41.00  148
  3  \w     35.00 120.00   0.50    0.08    --   47.95  48.00-169.00  170
  4  \w     94.00 174.00   0.50    0.34    --  107.11  48.00-169.00  160
  5  \w    -66.00  -9.00   0.50    0.08    --  -18.75 125.00 -30.00  114
  6  \w    -31.00  54.00   0.50    0.08    --  -18.75  48.00-169.00  170
  7  \w    -26.00  23.00   0.50    0.08    --   47.95 -19.00 -90.00   98
  8  \w     91.00 174.00   0.50    0.34    --  107.11  61.00  90.00  166
  9  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00  30.00   66
 10  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00-120.00   66
 11  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00 120.00   66
 12  \w     95.00 174.00   0.50    0.34    --  107.11  45.00 120.00  158
 13  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00   0.00   66
 14  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00 -90.00   66
 15  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00  60.00   66
 16  \w     92.00 174.00   0.50    0.34    --  107.11 125.00  30.00  164
 17  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00 -30.00   66
 18  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00  90.00   66
 19  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00-180.00   66
 20  \w     95.00 174.00   0.50    0.34    --  107.11  30.00-180.00  158
 21  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00 -60.00   66
 22  \w     35.00  68.00   0.50    0.34    --  107.11 -61.00-150.00   66
 23  \w     26.00 120.00   0.50    0.08    --   47.95  77.00-120.00  188
 24  \w     -4.00  82.00   0.50    0.08    --   47.95 -99.00-150.00  172
 25  \w     33.00 120.00   0.50    0.08    --   47.95  57.00 -30.00  174
 26  \w     26.00 120.00   0.50    0.08    --   47.95  77.00 -30.00  188
 27  \w     26.00 120.00   0.50    0.08    --   47.95  77.00  90.00  188
 28  \w     33.00 120.00   0.50    0.08    --   47.95  57.00  60.00  174
 29  \w     94.00 174.00   0.50    0.34    --  107.11  15.00   0.00  160
 30  \w     95.00 174.00   0.50    0.34    --  107.11  30.00-120.00  158
 31  \w     35.00 109.00   0.50    0.34    --  107.11 -94.00   0.00  148
 32  \w     95.00 174.00   0.50    0.34    --  107.11  45.00 -60.00  158
 33  \w     35.00 117.00   0.50    0.34    --  107.11-125.00-150.00  164
 34  \w     94.00 174.00   0.50    0.34    --  107.11  15.00  60.00  160
 35  \w     95.00 145.00   0.50    0.34    --  107.11  45.00   0.00  100
 36  \w     95.00 174.00   0.50    0.34    --  107.11  30.00 -90.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1209425000
_diffrn_orient_matrix_UB_12      0.0218264000
_diffrn_orient_matrix_UB_13      0.0123954000
_diffrn_orient_matrix_UB_21      -0.0015500000
_diffrn_orient_matrix_UB_22      -0.0442076000
_diffrn_orient_matrix_UB_23      -0.0693153000
_diffrn_orient_matrix_UB_31      -0.0399174000
_diffrn_orient_matrix_UB_32      0.0677854000
_diffrn_orient_matrix_UB_33      -0.0491950000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0252
_diffrn_reflns_av_unetI/netI     0.0115
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            33030
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.056
_diffrn_reflns_theta_min         4.376
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.970
_exptl_absorpt_correction_T_max  0.79555
_exptl_absorpt_correction_T_min  0.78641
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (Rigaku Oxford Diffraction, 2019)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.171
_exptl_crystal_description       block
_exptl_crystal_F_000             1608
_exptl_crystal_size_max          0.331
_exptl_crystal_size_mid          0.284
_exptl_crystal_size_min          0.259
_refine_diff_density_max         0.418
_refine_diff_density_min         -0.300
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     270
_refine_ls_number_reflns         4421
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0398
_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^)+(0.0572P)^2^+3.7086P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1104
_refine_ls_wR_factor_ref         0.1110
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4256
_reflns_number_total             4421
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1gc00388g2.cif
_cod_data_source_block           19ma071c2_sb673
_cod_depositor_comments
'Adding full bibliography for 7242639--7242644.cif.'
_cod_database_code               7242640
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.787
_shelx_estimated_absorpt_t_min   0.740
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-C15 \\sim C14-C15A
 with sigma of 0.02
 C14-C17 \\sim C14-C17A
 with sigma of 0.02
 C14-C16 \\sim C14-C16A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C15 \\sim C17 \\sim C16 \\sim C15A \\sim C16A \\sim C17A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C14, C15, C17, C16, C15A, C16A, C17A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=
 Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(1)
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B)
6.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9)
6.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,
 H13C), C21(H21A,H21B,H21C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C16(H16A,
 H16B,H16C), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              76851
_olex2_submission_special_instructions 'No special instructions were received'