Nitrogen–nitrogen-functionalized N-heterocyclic carbene ruthenium(ii) complexes realized efficient CO2 hydrogenation to formate
Gong, Huihua; Cui, Tianhua; Liu, Zheyuan; Zheng, Yanling; Zheng, Xueli; Fu, Haiyan; Yuan, Maolin; Chen, Hua; Xu, Jiaqi; Li, Ruixiang; Catalysis Science & Technology 12 (2022) 6213–6218; doi:10.1039/D2CY00741J

data_1567564
_publ_section_title
;
 Nitrogen--nitrogen-functionalized N-heterocyclic carbene ruthenium(ii)
 complexes realized efficient CO2 hydrogenation to formate
;
_journal_issue                   20
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              6213
_journal_page_last               6218
_journal_paper_doi               10.1039/D2CY00741J
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety         'Cl, C31 H32 N4 O P Ru'
_chemical_formula_sum            'C31 H32 Cl N4 O P Ru'
_chemical_formula_weight         644.09
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-11-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-12-02 deposited with the CCDC.	2022-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                106.120(4)
_cell_angle_beta                 103.920(3)
_cell_angle_gamma                103.786(3)
_cell_formula_units_Z            8
_cell_length_a                   17.5755(6)
_cell_length_b                   19.7613(8)
_cell_length_c                   21.9822(9)
_cell_measurement_reflns_used    12936
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      29.0520
_cell_measurement_theta_min      3.3030
_cell_volume                     6727.3(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0874
_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    -82.00  11.60   0.60   50.00    --  -14.81 -77.00 -90.00  156
  2  \w    -18.00  24.00   0.60   50.00    --  -14.81 -99.00 150.00   70
  3  \w    -42.00  50.40   0.60   50.00    --  -14.81  77.00  30.00  154
  4  \w    -46.00  35.60   0.60   50.00    --   17.00 -19.00 150.00  136
  5  \w     -2.00  85.60   0.60   50.00    --   17.00  38.00-180.00  146
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0214583000
_diffrn_orient_matrix_UB_12      0.0029467000
_diffrn_orient_matrix_UB_13      -0.0304037000
_diffrn_orient_matrix_UB_21      0.0229381000
_diffrn_orient_matrix_UB_22      -0.0189063000
_diffrn_orient_matrix_UB_23      -0.0166619000
_diffrn_orient_matrix_UB_31      -0.0308127000
_diffrn_orient_matrix_UB_32      -0.0346005000
_diffrn_orient_matrix_UB_33      -0.0079269000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0409
_diffrn_reflns_av_unetI/netI     0.0694
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            57446
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.938
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.620
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91906
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.272
_exptl_crystal_F_000             2640
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.05
_refine_diff_density_max         5.545
_refine_diff_density_min         -1.051
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1377
_refine_ls_number_reflns         27454
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1274
_refine_ls_R_factor_gt           0.0962
_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^)+(0.1374P)^2^+43.2432P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2659
_refine_ls_wR_factor_ref         0.2852
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18177
_reflns_number_total             27454
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cy00741j2.cif
_cod_data_source_block           191105_s3_ghh
_cod_depositor_comments
'Adding full bibliography for 1567562--1567564.cif.'
_cod_original_cell_volume        6727.2(5)
_cod_database_code               1567564
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         c12h12n2o3p1c
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.812
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C29B) = Uanis(C28B) = Uanis(C27B)
Uanis(C14C) = Uanis(C15C) = Uanis(C17C) = Uanis(C16C) = Uanis(C18C) =
Uanis(C20C)
Uanis(C10A) = Uanis(C9A)
3.a Ternary CH refined with riding coordinates:
 N3A(H3A), N3D(H3D), N3C(H3C), N3B(H3B)
3.b Secondary CH2 refined with riding coordinates:
 C5A(H5AA,H5AB), C6A(H6AA,H6AB), C7A(H7AA,H7AB), C5D(H5DA,H5DB), C6D(H6DA,
 H6DB), C7D(H7DA,H7DB), C5C(H5CA,H5CB), C6C(H6CA,H6CB), C7C(H7CA,H7CB),
 C5B(H5BA,H5BB), C6B(H6BA,H6BB), C7B(H7BA,H7BB)
3.c Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3AA), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C14A(H14A),
  C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A), C20A(H20A), C21A(H21A),
 C22A(H22A), C23A(H23A), C24A(H24A), C26A(H26A), C27A(H27A), C28A(H28A),
 C29A(H29A), C30A(H30A), C2D(H2D), C3D(H3DA), C9D(H9D), C10D(H10D), C11D(H11D),
 C12D(H12D), C14D(H14D), C15D(H15D), C16D(H16D), C17D(H17D), C18D(H18D),
 C20D(H20D), C21D(H21D), C22D(H22D), C23D(H23D), C24D(H24D), C26D(H26D),
 C27D(H27D), C28D(H28D), C29D(H29D), C30D(H30D), C2C(H2C), C3C(H3CA), C9C(H9C),
 C10C(H10C), C11C(H11C), C12C(H12C), C14C(H14C), C15C(H15C), C16C(H16C),
 C17C(H17C), C18C(H18C), C20C(H20C), C21C(H21C), C22C(H22C), C23C(H23C),
 C24C(H24C), C26C(H26C), C27C(H27C), C28C(H28C), C29C(H29C), C30C(H30C),
 C2B(H2B), C3B(H3BA), C9B(H9B), C10B(H10B), C11B(H11B), C12B(H12B), C14B(H14B),
 C15B(H15B), C16B(H16B), C17B(H17B), C18B(H18B), C20B(H20B), C21B(H21B),
 C22B(H22B), C23B(H23B), C24B(H24B), C26B(H26B), C27B(H27B), C28B(H28B),
 C29B(H29B), C30B(H30B)
3.d Idealised Me refined as rotating group:
 C4A(H4AA,H4AB,H4AC), C4D(H4DA,H4DB,H4DC), C4C(H4CA,H4CB,H4CC), C4B(H4BA,H4BB,
 H4BC)
;
_shelx_res_checksum              13362
_olex2_date_sample_data_collection 2019-11-05
_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 1.066
_oxdiff_exptl_absorpt_empirical_full_min 0.944