Ruthenium-catalyzed Hydrogenation of CO2 as a Route to Methyl Esters for use as Biofuels or fine Chemicals
Wang, Zheng; Zhao, Ziwei; Li, Yong; Zhong, Yanxia; Zhang, Qiuyue; Liu, Qingbin; Solan, Gregory; Ma, Yanping; Sun, Wen Hua; Chemical Science  (2020) –; doi:10.1039/D0SC02942D

data_1558258
_publ_section_title
;
 Ruthenium-catalyzed Hydrogenation of CO2 as a Route to Methyl Esters for
 use as Biofuels or fine Chemicals
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02942D
_journal_year                    2020
_chemical_formula_moiety         'C52 H55 Cl O P3 Ru, Cl O4'
_chemical_formula_sum            'C52 H55 Cl2 O5 P3 Ru'
_chemical_formula_weight         1024.90
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-23
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-10-29 deposited with the CCDC.	2020-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.75(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.968(4)
_cell_length_b                   12.863(3)
_cell_length_c                   19.229(4)
_cell_measurement_reflns_used    14445
_cell_measurement_temperature    173
_cell_measurement_theta_max      27.4854
_cell_measurement_theta_min      1.3040
_cell_volume                     4753.5(19)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173
_diffrn_measured_fraction_theta_full 0.9973
_diffrn_measured_fraction_theta_max 0.9973
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            61939
_diffrn_reflns_theta_full        27.4957
_diffrn_reflns_theta_max         27.50
_diffrn_reflns_theta_min         1.93
_exptl_absorpt_coefficient_mu    0.591
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.87673
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear brownish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.4320
_exptl_crystal_description       plate
_exptl_crystal_F_000             2118.2341
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.425
_exptl_crystal_size_min          0.278
_refine_diff_density_max         0.8415
_refine_diff_density_min         -0.7446
_refine_diff_density_rms         0.0720
_refine_ls_d_res_high            0.7697
_refine_ls_d_res_low             10.5626
_refine_ls_goodness_of_fit_ref   1.0397
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    99
_refine_ls_number_parameters     609
_refine_ls_number_reflns         10887
_refine_ls_number_restraints     56
_refine_ls_restrained_S_all      1.0369
_refine_ls_R_factor_all          0.0363
_refine_ls_R_factor_gt           0.0356
_refine_ls_shift/su_max          0.0003
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0370P)^2^+5.7746P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0844
_refine_ls_wR_factor_ref         0.0851
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              24
_reflns_limit_h_min              -25
_reflns_limit_k_max              16
_reflns_limit_k_min              0
_reflns_limit_l_max              24
_reflns_limit_l_min              0
_reflns_number_gt                10690
_reflns_number_total             10887
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d0sc02942d2.cif
_cod_data_source_block           Ru3
_cod_original_cell_volume        4753.6(18)
_cod_database_code               1558258
_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
 Cl2-O2A = Cl2-O2 = Cl2-O5A = Cl2-O5 = Cl2-O4A = Cl2-O4 = Cl2-O3 = Cl2-O3A
 1.42 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O4A \\sim O4 \\sim O3 \\sim O3A \\sim O2A \\sim O2 \\sim O5A \\sim O5: within
1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O2A) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O5A) \\sim Ueq, Uanis(O5)
\\sim Ueq, Uanis(O4A) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O3) \\sim Ueq,
Uanis(O3A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(O5A)=Sof(O4A)=Sof(O2A)=Sof(O3A)=1-FVAR(1)
 Sof(O2)=Sof(O3)=Sof(O4)=Sof(O5)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C50(H50)
5.b Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C15(H15a,H15b), C17(H17a,H17b), C30(H30a,H30b)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26),
  C27(H27), C28(H28), C29(H29), C32(H32), C33(H33), C34(H34), C35(H35),
 C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C45(H45),
  C47(H47), C48(H48)
5.d Idealised Me refined as rotating group:
 C16(H16a,H16b,H16c), C49(H49a,H49b,H49c), C51(H51a,H51b,H51c), C52(H52a,H52b,
 H52c)
;
_olex2_submission_special_instructions 'No special instructions were received'