Two step activation of Ru-PN3P pincer catalysts for CO2 hydrogenation
Tossaint, Alex S.; Rebreyend, Christophe; Sinha, Vivek; Weber, Manuela; Canossa, Stefano; Pidko, Evgeny A.; Filonenko, Georgy A.; Catalysis Science & Technology 12 (2022) 2972–2977; doi:10.1039/D2CY00485B

data_1566663
_publ_section_title
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 Two step activation of Ru-PN3P pincer catalysts for CO2 hydrogenation
;
_journal_issue                   9
_journal_name_full               'Catalysis Science &amp; Technology'
_journal_page_first              2972
_journal_page_last               2977
_journal_paper_doi               10.1039/D2CY00485B
_journal_volume                  12
_journal_year                    2022
_chemical_formula_moiety         'C36 H37 K N3 O3 P2 Ru S'
_chemical_formula_sum            'C36 H37 K N3 O3 P2 Ru S'
_chemical_formula_weight         793.85
_chemical_name_systematic
'Potassium (hydrido carbonyl dimethylsulfoxido N,N\"i>?-bis(diphenylphosphino)-2,6-diamidopyridino ruthenate (II))'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-12-01
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_audit_update_record
;
2021-12-01 deposited with the CCDC.	2022-03-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6529(5)
_cell_length_b                   18.7504(6)
_cell_length_c                   15.5836(5)
_cell_measurement_reflns_used    13980
_cell_measurement_temperature    104.90
_cell_measurement_theta_max      75.0
_cell_measurement_theta_min      3.2
_cell_volume                     3697.2(2)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      104.90
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0645
_diffrn_reflns_av_unetI/netI     0.0380
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            63330
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.587
_diffrn_reflns_theta_min         2.356
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    6.093
_exptl_absorpt_correction_T_max  0.7538
_exptl_absorpt_correction_T_min  0.4451
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2016/2'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.426
_exptl_crystal_description       plate
_exptl_crystal_F_000             1628
_exptl_crystal_recrystallization_method
'counterdiffusion of antisolvent (diethylether) in a THF solution'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.566
_refine_diff_density_min         -0.675
_refine_diff_density_rms         0.101
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.05(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     458
_refine_ls_number_reflns         7434
_refine_ls_number_restraints     275
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0600
_refine_ls_R_factor_gt           0.0521
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0766P)^2^+8.0585P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1374
_refine_ls_wR_factor_ref         0.1467
_reflns_Friedel_coverage         0.923
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                6655
_reflns_number_total             7434
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cy00485b2.cif
_cod_data_source_block           gfe1347_b
_cod_depositor_comments
'Adding full bibliography for 1566663--1566665.cif.'
_cod_database_code               1566663
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.838
_shelx_estimated_absorpt_t_min   0.581
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.95(2)
 0.05(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C31-C30 = C32-C33
 1.5 with sigma of 0.02
 C32-C33
 1.48 with sigma of 0.02
 O3-C33
 1.41 with sigma of 0.02
 O3-C30
 1.42 with sigma of 0.02
 C30-C31
 1.5 with sigma of 0.02
 O3-C30 = O3-C33
 1.42 with sigma of 0.02
 O3-C32 = O3-C31
 2.37 with sigma of 0.04
 C30-C33
 2.35 with sigma of 0.04
 O3-C31
 2.37 with sigma of 0.04
 O3-C32
 2.37 with sigma of 0.04
 C32-C33 \\sim C30-C31
 with sigma of 0.02
 O3-C33 \\sim O3-C30
 with sigma of 0.02
 C32-O3 \\sim O3-C31
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
C3B \\sim C4B \\sim C5B \\sim C6B \\sim C1B \\sim C2B: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C3A \\sim C4A \\sim C5A \\sim C6A \\sim C1A \\sim C2A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
O3 \\sim C32 \\sim C33 \\sim C30 \\sim C31: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C2B, C1B, C3B, C4B, C5B, C6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5A, C6A, C1A, C4A, C3A, C2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3B, C2B, C1B, C6B, C5B, C4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3A, C2A, C4A, C5A, C6A, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17, C18, C13, C14, C15, N1, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3B, C4B, C5B, C6B, C2B, C1B, P1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, C32, C33, C30, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33, O3, C30, C31, C32, K1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C2A)=Sof(H2A)=Sof(C1A)=Sof(C6A)=Sof(H6A)=Sof(C5A)=Sof(H5A)=Sof(C4A)=
 Sof(H4A)=Sof(C3A)=Sof(H3A)=1-FVAR(1)
 Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=
 Sof(C6B)=Sof(H6B)=Sof(C1B)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C33(H33A,H33B), C30(H30A,H30B), C31(H31A,H31B)
7.b Aromatic/amide H refined with riding coordinates:
 C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B), C6B(H6B), C9(H9), C28(H28), C23(H23),
 C11(H11), C12(H12), C24(H24), C22(H22), C14(H14), C16(H16), C20(H20), C8(H8),
 C17(H17), C18(H18), C15(H15), C21(H21), C10(H10), C27(H27), C26(H26), C2A(H2A),
  C6A(H6A), C5A(H5A), C4A(H4A), C3A(H3A)
7.c Fitted hexagon refined as free rotating group:
 C2B(C3B,C4B,C5B,C6B,C1B), C2A(C1A,C6A,C5A,C4A,C3A)
7.d Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              88612
_olex2_exptl_crystal_mounting_method 'cryo loop, in a cryo oil droplet'
_olex2_submission_special_instructions 'No special instructions were received'