Enhanced Hydrogenation of Carbon Dioxide to Methanol by a Ruthenium Complex with a Charged Outer-Coordination Sphere
Erickson, Jeremy D.; Preston, Andrew Z.; Linehan, John C.; Wiedner, Eric S.; ACS Catalysis 10 (2020) 7419–7423; doi:10.1021/acscatal.0c02268

data_4517796
_publ_section_title
;
 Enhanced Hydrogenation of Carbon Dioxide to Methanol by a Ruthenium
 Complex with a Charged Outer-Coordination Sphere
;
_journal_issue                   13
_journal_name_full               'ACS Catalysis'
_journal_page_first              7419
_journal_page_last               7423
_journal_paper_doi               10.1021/acscatal.0c02268
_journal_volume                  10
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C46 H48 N4 P3 Ru, 3(C F3 O3 S), C2 H3 N'
_chemical_formula_sum            'C51 H51 F9 N5 O9 P3 Ru S3'
_chemical_formula_weight         1339.12
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-01-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-01-31 deposited with the CCDC.	2020-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6221(6)
_cell_length_b                   20.3106(10)
_cell_length_c                   22.3941(10)
_cell_measurement_reflns_used    9973
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      32.56
_cell_measurement_theta_min      2.63
_cell_volume                     5741.0(5)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            222364
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.598
_diffrn_reflns_theta_min         2.077
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.553
_exptl_absorpt_correction_T_max  0.4293
_exptl_absorpt_correction_T_min  0.3746
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1093 before and 0.0555 after correction. The Ratio of minimum to maximum transmission is 0.8726. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.549
_exptl_crystal_description       needle
_exptl_crystal_F_000             2728
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexanes, acetonitrile'
_exptl_crystal_size_max          0.513
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.058
_refine_diff_density_max         1.360
_refine_diff_density_min         -0.951
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Flack x determined using 8630 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     755
_refine_ls_number_reflns         20904
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0455P)^2^+5.2525P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0931
_refine_ls_wR_factor_ref         0.0950
_reflns_Friedel_coverage         0.846
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                19882
_reflns_number_total             20904
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c02268_si_002.cif
_cod_data_source_block           jde87_01_final_a
_cod_depositor_comments
;Adding full bibliography for 4517796.cif.

 Adding full bibliography for 4517796.cif.
;
_cod_database_code               4517796
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.765
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C48-F7 \\sim C48-F9 \\sim C48-F8
 with sigma of 0.1
 S3-O9 \\sim S3-O8 \\sim S3-O7
 with sigma of 0.1
 S3-O7 \\sim S3A-O7A
 with sigma of 0.02
 S3-O8 \\sim S3A-O8A
 with sigma of 0.02
 S3-O9 \\sim S3A-O9A
 with sigma of 0.02
 S3-C48 \\sim S3A-C48A
 with sigma of 0.02
 F7-C48 \\sim F7A-C48A
 with sigma of 0.02
 F8-C48 \\sim F8A-C48A
 with sigma of 0.02
 F9-C48 \\sim F9A-C48A
 with sigma of 0.02
 S3-F7 \\sim S3A-F7A
 with sigma of 0.04
 S3-F8 \\sim S3A-F8A
 with sigma of 0.04
 S3-F9 \\sim S3A-F9A
 with sigma of 0.04
 O7-O8 \\sim O7A-O8A
 with sigma of 0.04
 O7-O9 \\sim O7A-O9A
 with sigma of 0.04
 O7-C48 \\sim O7A-C48A
 with sigma of 0.04
 O8-O9 \\sim O8A-O9A
 with sigma of 0.04
 O8-C48 \\sim O8A-C48A
 with sigma of 0.04
 O9-C48 \\sim O9A-C48A
 with sigma of 0.04
 F7-F8 \\sim F7A-F8A
 with sigma of 0.04
 F7-F9 \\sim F7A-F9A
 with sigma of 0.04
 F8-F9 \\sim F8A-F9A
 with sigma of 0.04
 C11-C12 \\sim C11-C12A
 with sigma of 0.02
 C12-C13 \\sim C12A-C13A
 with sigma of 0.02
 C13-C14 \\sim C13A-C14A
 with sigma of 0.02
 C11-C13 \\sim C11-C13A
 with sigma of 0.04
 C12-C14 \\sim C12A-C14A
 with sigma of 0.04
3. Others
 Sof(H15A)=Sof(C14A)=Sof(H14A)=Sof(C13A)=Sof(H13A)=Sof(C12A)=Sof(H12A)=1-FVAR(1)
 Sof(H15)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=FVAR(1)
 Fixed Sof: S3(0.75) O7(0.75) O8(0.75) O9(0.75) F7(0.75) F8(0.75) F9(0.75)
 C48(0.75) S3A(0.25) O7A(0.25) O8A(0.25) O9A(0.25) C48A(0.25) F7A(0.25)
 F9A(0.25) F8A(0.25)
4.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
4.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C15(H15), C15(H15A), C16(H16),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26),
  C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34),
 C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C12(H12), C13(H13), C14(H14),
  C14A(H14A), C13A(H13A), C12A(H12A)
4.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C46(H46A,H46B,
 H46C), C51(H51A,H51B,H51C)
;
_olex2_submission_special_instructions 'No special instructions were received'