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_1569547
_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 H31 N4 Ru, C F3 O3 S'
_chemical_formula_sum            'C32 H31 F3 N4 O3 Ru S'
_chemical_formula_weight         709.74
_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   geom
_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                 100.5586(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.9076(3)
_cell_length_b                   11.49805(18)
_cell_length_c                   14.5081(2)
_cell_measurement_reflns_used    20877
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      77.289
_cell_measurement_theta_min      2.382
_cell_volume                     3100.66(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 0.986
_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    -81.00 -30.00   0.50    3.20    --  -24.75 140.00 176.00  102
  2  \w    -47.00 -16.00   0.50    3.20    --  -24.75 130.00   3.00   62
  3  \w    -78.00 -53.00   0.50    3.20    --  -24.75 130.00   3.00   50
  4  \w     58.00  91.00   0.50    3.20    --   43.26-130.00 -68.00   66
  5  \w     43.00  68.00   0.50    3.20    --   43.26-140.00 118.00   50
  6  \w     93.00 141.00   0.50   10.00    --  113.13 130.00   3.00   96
  7  \w     90.00 116.00   0.50   10.00    --  113.13-130.00 -68.00   52
  8  \w    104.00 141.00   0.50   10.00    --  113.13 140.00 176.00   74
  9  \w    -99.00 -70.00   0.50    3.20    --  -24.75 -61.00-120.00   58
 10  \w    -62.00 -23.00   0.50    3.20    --  -24.75 -61.00-120.00   78
 11  \w     81.00 106.00   0.50    3.20    --   43.26-140.00 118.00   50
 12  \w    -29.00  65.00   0.50    3.20    --   43.26 -77.00-180.00  188
 13  \w      9.00  34.00   0.50    3.20    --   43.26  89.00   1.66   50
 14  \w     46.00  72.00   0.50    3.20    --   43.26 -77.00  60.00   52
 15  \w    -11.00  23.00   0.50    3.20    --   43.26 -19.00 -30.00   68
 16  \w     23.00 120.00   0.50    3.20    --   43.26  38.00-150.00  194
 17  \w    -24.00  16.00   0.50    3.20    --   43.26 -19.00 -60.00   80
 18  \w    -34.00  23.00   0.50    3.20    --   43.26 -19.00 -90.00  114
 19  \w     12.00  38.00   0.50    3.20    --   43.26 -77.00  60.00   52
 20  \w    -14.00  23.00   0.50    3.20    --   43.26 -19.00-150.00   74
 21  \w    104.00 175.00   0.50   10.00    --  113.13  45.00-150.00  142
 22  \w    129.00 170.00   0.50   10.00    --  113.13  77.00-180.00   82
 23  \w     40.00  66.00   0.50   10.00    --  113.13 -61.00 120.00   52
 24  \w     39.00  67.00   0.50   10.00    --  113.13 -61.00  60.00   56
 25  \w     97.00 174.00   0.50   10.00    --  113.13 125.00  60.00  154
 26  \w     39.00  64.00   0.50   10.00    --  113.13 -61.00-120.00   50
 27  \w     93.00 160.00   0.50   10.00    --  113.13  45.00 120.00  134
 28  \w     41.00  67.00   0.50   10.00    --  113.13 -61.00  30.00   52
 29  \w     92.00 172.00   0.50   10.00    --  113.13  34.00 153.71  160
 30  \w     40.00  92.00   0.50   10.00    --  113.13 -94.00 120.00  104
 31  \w     39.00  65.00   0.50   10.00    --  113.13 -61.00 -60.00   52
 32  \w     47.00 109.00   0.50   10.00    --  113.13-125.00  60.00  124
 33  \w     97.00 164.00   0.50   10.00    --  113.13 125.00-150.00  134
 34  \w     41.00  66.00   0.50   10.00    --  113.13 -61.00 -30.00   50
 35  \w     79.00 104.00   0.50   10.00    --  113.13 -94.00-180.00   50
 36  \w     41.00  67.00   0.50   10.00    --  113.13 -94.00-180.00   52
 37  \w     92.00 118.00   0.50   10.00    --  113.13  77.00  60.00   52
 38  \w    131.00 169.00   0.50   10.00    --  113.13  77.00  60.00   76
 39  \w     99.00 177.00   0.50   10.00    --  113.13  30.00-180.00  156
 40  \w    127.00 167.00   0.50   10.00    --  113.13 125.00 150.00   80
 41  \w     40.00  69.00   0.50   10.00    --  113.13-125.00  30.00   58
 42  \w     51.00 106.00   0.50   10.00    --  113.13 -95.00 -53.26  110
 43  \w     92.00 176.00   0.50   10.00    --  113.13  77.00-120.00  168
 44  \w     41.00  69.00   0.50   10.00    --  113.13 -94.00-150.00   56
 45  \w     78.00 104.00   0.50   10.00    --  113.13 -94.00-150.00   52
 46  \w     44.00 106.00   0.50   10.00    --  113.13-102.00 158.69  124
 47  \w     49.00  84.00   0.50   10.00    --  113.13-125.00   0.00   70
 48  \w     95.00 121.00   0.50   10.00    --  113.13-140.00 118.00   52
;
_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      -0.0699941
_diffrn_orient_matrix_UB_12      -0.0662302
_diffrn_orient_matrix_UB_13      0.005113
_diffrn_orient_matrix_UB_21      0.0442184
_diffrn_orient_matrix_UB_22      -0.1082482
_diffrn_orient_matrix_UB_23      0.0371023
_diffrn_orient_matrix_UB_31      0.00351
_diffrn_orient_matrix_UB_32      0.0430123
_diffrn_orient_matrix_UB_33      0.1013178
_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  0.0682
_diffrn_reflns_av_unetI/netI     0.024
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            12137
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.815
_diffrn_reflns_theta_min         2.377
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.22
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.76669
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.52
_exptl_crystal_description       plate
_exptl_crystal_F_000             1448
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.154
_exptl_crystal_size_min          0.049
_refine_diff_density_max         2.13
_refine_diff_density_min         -0.974
_refine_diff_density_rms         0.2
_refine_ls_extinction_coef       0.0028(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.203
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     458
_refine_ls_number_reflns         12137
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.203
_refine_ls_R_factor_all          0.0818
_refine_ls_R_factor_gt           0.0766
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1999P)^2^+2.7059P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2636
_refine_ls_wR_factor_ref         0.2785
_reflns_Friedel_coverage         0
_reflns_number_gt                10974
_reflns_number_total             12137
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9904\% 
around [-0.23 -0.00 0.97] (reciprocal) or [0.00 0.00 1.00] (direct)
;
_cod_data_source_file            d3cy00512g2.cif
_cod_data_source_block           21MA010_PK315
_cod_depositor_comments
'Adding full bibliography for 1569547--1569548.cif.'
_cod_original_cell_volume        3100.67(9)
_cod_database_code               1569547
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_shelx_estimated_absorpt_t_min   0.393
_shelx_estimated_absorpt_t_max   0.784
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.473
_oxdiff_exptl_absorpt_empirical_full_min 0.717
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
        1. Twinned data refinement
 Scales: 0.561(2)
 0.439(2)
        2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        3. Uiso/Uaniso restraints and constraints
Uanis(C32A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
        4. Others
 Sof(F2A)=Sof(C32A)=Sof(F1A)=Sof(F3A)=Sof(O3A)=Sof(O2A)=1-FVAR(1)
 Sof(O2)=Sof(O3)=Sof(F2)=Sof(F1)=Sof(C32)=Sof(F3)=FVAR(1)
        5.a Ternary CH refined with riding coordinates:
 C29(H29)
        5.b Aromatic/amide H refined with riding coordinates:
 C26(H26), C23(H23), C17(H17), C24(H24), C18(H18), C19(H19), C27(H27),
 C14(H14), C1(H1), C20(H20), C6(H6), C5(H5), C7(H7), C11(H11), C2(H2), C12(H12),
  C13(H13), C3(H3)
        5.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C31(H31A,H31B,H31C), C21(H21A,H21B,H21C), C30(H30A,H30B,
 H30C)
;
_shelx_res_checksum              93202