Efficient additive-free formic acid dehydrogenation with a NNN–ruthenium complex
Knörr, Pascal; Lentz, Nicolas; Albrecht, Martin; Catalysis Science & Technology 13 (2023) 5625–5631; doi:10.1039/D3CY00512G

data_1569548
_publ_section_title
;
 Efficient additive-free formic acid dehydrogenation with a NNN--ruthenium
 complex
;
_journal_issue                   19
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              5625
_journal_page_last               5631
_journal_paper_doi               10.1039/D3CY00512G
_journal_volume                  13
_journal_year                    2023
_chemical_formula_moiety         'C31 H32 N4 Ru, 2(F6 P), C H2 Cl2'
_chemical_formula_sum            'C32 H34 Cl2 F12 N4 P2 Ru'
_chemical_formula_weight         936.54
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_update_record
;
2023-03-23 deposited with the CCDC.	2023-07-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.7636(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.26618(17)
_cell_length_b                   10.02851(8)
_cell_length_c                   20.44489(17)
_cell_measurement_reflns_used    25476
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      27.844
_cell_measurement_theta_min      2.023
_cell_volume                     4067.94(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0965
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 0.993
_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     39.00 122.00   1.00   25.00    --   27.49 178.00 -30.00   83
  2  \w    -16.00  42.00   1.00   25.00    --   27.49  77.00  30.00   58
  3  \w    -15.00  83.00   1.00   25.00    --   27.49 -99.00  90.00   98
  4  \w    -16.00  42.00   1.00   25.00    --   27.49  77.00  90.00   58
  5  \w     39.00 122.00   1.00   25.00    --   27.49 178.00-120.00   83
  6  \w    -49.00  65.00   1.00   25.00    --   27.49 -57.00 -90.00  114
  7  \w    -57.00 115.00   1.00   25.00    --   27.49  19.00 -90.00  172
  8  \w    -16.00  15.00   1.00   25.00    --   27.49  77.00-120.00   31
  9  \w    -28.00 109.00   1.00   25.00    --   27.49  38.00  30.00  137
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.023351
_diffrn_orient_matrix_UB_12      0.0532832
_diffrn_orient_matrix_UB_13      -0.0019523
_diffrn_orient_matrix_UB_21      -0.0138926
_diffrn_orient_matrix_UB_22      -0.0171971
_diffrn_orient_matrix_UB_23      -0.0336311
_diffrn_orient_matrix_UB_31      -0.0232449
_diffrn_orient_matrix_UB_32      -0.0432207
_diffrn_orient_matrix_UB_33      0.0109639
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            49828
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.094
_diffrn_reflns_theta_min         2.035
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.679
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.86403
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.529
_exptl_crystal_description       plate
_exptl_crystal_F_000             1880
_exptl_crystal_size_max          0.316
_exptl_crystal_size_mid          0.216
_exptl_crystal_size_min          0.095
_refine_diff_density_max         0.831
_refine_diff_density_min         -0.692
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     533
_refine_ls_number_reflns         8903
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0397
_refine_ls_R_factor_gt           0.0334
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0373P)^2^+5.1184P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0836
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0
_reflns_number_gt                7760
_reflns_number_total             8903
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy00512g2.cif
_cod_data_source_block           21MA042_PK340
_cod_depositor_comments
'Adding full bibliography for 1569547--1569548.cif.'
_cod_database_code               1569548
_shelx_estimated_absorpt_t_min   0.814
_shelx_estimated_absorpt_t_max   0.938
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.138
_oxdiff_exptl_absorpt_empirical_full_min 0.84
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
        1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        2. Uiso/Uaniso restraints and constraints
Cl2A \\sim Cl2: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
        0.008 within 1.7A
Uanis(Cl2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
        3. Others
 Sof(H32C)=Sof(H32D)=Sof(Cl2A)=1-FVAR(1)
 Sof(Cl2)=Sof(H32A)=Sof(H32B)=FVAR(1)
 Sof(F11A)=Sof(F12A)=Sof(F10A)=Sof(F9A)=1-FVAR(2)
 Sof(F12)=Sof(F11)=Sof(F9)=Sof(F10)=FVAR(2)
        4.a Ternary CH refined with riding coordinates:
 C29(H29)
        4.b Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C32(H32C,H32D)
        4.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C14(H14), C11(H11), C27(H27), C1(H1), C24(H24), C23(H23), C17(H17),
 C12(H12), C20(H20), C7(H7), C5(H5), C19(H19), C18(H18), C3(H3), C2(H2A),
 C13(H13), C6(H6)
        4.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C21(H21A,H21B,H21C), C31(H31A,H31B,
 H31C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              37354
_shelx_fab_checksum              13403