Phosphine-free Ru(ii)–CNC pincer complexes with mixed protic- and classical-NHCs in the same molecule for hydrogen production via oxidant-free benzyl alcohol dehydrogenation to benzoic acids
Srivastava, Navdeep; Meena, Rohitash; Singh, Amrendra K.; New Journal of Chemistry 48 (2024) 17071–17082; doi:10.1039/D4NJ03172E

data_7063438
_publ_section_title
;
 Phosphine-free Ru(ii)--CNC pincer complexes with mixed protic- and
 classical-NHCs in the same molecule for hydrogen production via
 oxidant-free benzyl alcohol dehydrogenation to benzoic acids
;
_journal_issue                   39
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              17071
_journal_page_last               17082
_journal_paper_doi               10.1039/D4NJ03172E
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety         'C32 H36 Cl0.147 I0.853 N8 Ru, F6 P, C H4 O'
_chemical_formula_sum            'C33 H40 Cl0.15 F6 I0.86 N8 O P Ru'
_chemical_formula_weight         924.41
_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
_audit_creation_date             2024-09-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-04 deposited with the CCDC.	2024-09-09 downloaded from the CCDC.
;
_cell_angle_alpha                77.402(2)
_cell_angle_beta                 69.513(2)
_cell_angle_gamma                71.130(2)
_cell_formula_units_Z            2
_cell_length_a                   11.7722(3)
_cell_length_b                   12.5423(3)
_cell_length_c                   14.3998(4)
_cell_measurement_reflns_used    9458
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.8580
_cell_measurement_theta_min      3.4640
_cell_volume                     1871.37(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0309
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.876
_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     21.00  46.00   0.50   15.00    --   18.01-136.00 125.00   50
  2  \w     26.00  52.00   0.50   15.00    --   18.01-133.00 -56.00   52
  3  \w    -82.00 -57.00   0.50   15.00    --  -19.26 133.00  11.00   50
  4  \w    -82.00 -42.00   0.50   15.00    --  -19.26 136.00-170.00   80
  5  \w    -43.00 -17.00   0.50   15.00    --   18.01 -57.00 120.00   52
  6  \w    -48.00  90.00   0.50   15.00    --   18.01   0.00 120.00  276
  7  \w     -7.00  85.00   0.50   15.00    --   18.01  37.00-180.00  184
  8  \w    -20.00   6.00   0.50   15.00    --   18.01 -99.00 150.00   52
  9  \w     35.00  60.00   0.50   15.00    --   18.01 -99.00 150.00   50
 10  \w     62.00  94.00   0.50   15.00    --   18.01 178.00  60.00   64
 11  \w     37.00  62.00   0.50   15.00    --   18.01 178.00  30.00   50
 12  \w    -41.00  15.00   0.50   15.00    --  -19.26  77.00  60.00  112
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0484
_diffrn_reflns_av_unetI/netI     0.0653
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.876
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20121
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.876
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.005
_diffrn_reflns_theta_min         3.316
_exptl_absorpt_coefficient_mu    1.246
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63158
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic reddish red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.641
_exptl_crystal_description       block
_exptl_crystal_F_000             926
_exptl_crystal_preparation       Methanol
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.772
_refine_diff_density_min         -0.666
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     474
_refine_ls_number_reflns         8714
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0477
_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^)+(0.0504P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1048
_refine_ls_wR_factor_ref         0.1189
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6431
_reflns_number_total             8714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj03172e2.cif
_cod_data_source_block           red1
_cod_depositor_comments          'Adding full bibliography for 7063438.cif.'
_cod_database_code               7063438
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Restrained distances
 Ru1-I1 \\sim Ru1-Cl1
 with sigma of 0.02
2. Others
 Sof(Cl1)=1-FVAR(1)
 Sof(I1)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C14(H14), C17(H17), C19(H19), C30(H30)
3.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B), C20(H20A,
 H20B), C21(H21A,H21B)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C10(H10), C11(H11), C22(H22),
 C23(H23), C24(H24), C25(H25), C27(H27), C28(H28)
3.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1A)
;
_shelx_res_checksum              98932
_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
;