An efficient mixed-valence copper pyrazolate catalyst for the conversion of carbon dioxide and epoxides into cyclic carbonates
Wang, Jian-Ge; Liu, Yang; Liu, Chun-Mei; Chen, Jing-Huo; Yang, Guang; Dalton Transactions  (2023) –; doi:10.1039/D3DT00844D

data_7713206
_publ_section_title
;
 An efficient mixed-valence copper pyrazolate catalyst for the conversion
 of carbon dioxide and epoxides into cyclic carbonates
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00844D
_journal_year                    2023
_chemical_formula_moiety         'C45 H30 Cl3 Cu3 N6, C2 H3 N'
_chemical_formula_sum            'C47 H33 Cl3 Cu3 N7'
_chemical_formula_weight         992.77
_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             2023-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-20 deposited with the CCDC.	2023-05-29 downloaded from the CCDC.
;
_cell_angle_alpha                70.930(5)
_cell_angle_beta                 80.498(5)
_cell_angle_gamma                84.925(5)
_cell_formula_units_Z            2
_cell_length_a                   10.5699(8)
_cell_length_b                   14.0271(9)
_cell_length_c                   14.9724(8)
_cell_measurement_reflns_used    7879
_cell_measurement_temperature    120(10)
_cell_measurement_theta_max      28.5930
_cell_measurement_theta_min      3.0120
_cell_volume                     2067.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2116
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -29.00  61.00   1.00    4.73    --   18.94 -19.00   0.00   90
  2  \w     24.00  61.00   1.00    4.73    --   18.94 -99.00 120.00   37
  3  \w      8.00  37.00   1.00    4.73    --   18.94 -57.00 150.00   29
  4  \w    -48.00  -4.00   1.00    4.73    --   18.94 -57.00 150.00   44
  5  \w     -5.00  61.00   1.00    4.73    --   18.94 -99.00 -90.00   66
  6  \w    -48.00 -18.00   1.00    4.73    --   18.94 -37.00-180.00   30
  7  \w    -11.00  15.00   1.00    4.73    --   18.94  77.00 -60.00   26
  8  \w     47.00  87.00   1.00    4.73    --   18.94  77.00 -60.00   40
  9  \w    -10.00  44.00   1.00    4.73    --   18.94  77.00  30.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0286611000
_diffrn_orient_matrix_UB_12      -0.0463650000
_diffrn_orient_matrix_UB_13      0.0257283000
_diffrn_orient_matrix_UB_21      -0.0508250000
_diffrn_orient_matrix_UB_22      -0.0264310000
_diffrn_orient_matrix_UB_23      -0.0055540000
_diffrn_orient_matrix_UB_31      0.0350856000
_diffrn_orient_matrix_UB_32      -0.0042607000
_diffrn_orient_matrix_UB_33      -0.0432826000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0499
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            14600
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.910
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.767
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40079
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.594
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1004
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.520
_refine_diff_density_min         -0.390
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     542
_refine_ls_number_reflns         7283
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0415
_refine_ls_R_factor_gt           0.0337
_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^)+(0.0312P)^2^+0.8771P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0743
_refine_ls_wR_factor_ref         0.0791
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6266
_reflns_number_total             7283
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00844d2.cif
_cod_data_source_block           (CuIpz)3
_cod_database_code               7713206
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Cu'
_chemical_oxdiff_usercomment     CL+CU
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27),
  C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C36(H36),
 C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45)
2.b Idealised Me refined as rotating group:
 C47(H47A,H47B,H47C)
;
_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 2.743
_oxdiff_exptl_absorpt_empirical_full_min 0.689