Ambient-pressure selective hydrogenation of unsaturated aldehydes and ketones into unsaturated alcohols in the water phase.
Wang, Tao; Li, Bin; Zhang, Yu; Xu, Shuting; Wang, Jun; Zheng, Jianwei; Li, Hao; Zhang, Fengjun; Fang, Xiaolong; Dalton transactions (Cambridge, England : 2003) 54 (2025) 1791–1796; doi:10.1039/d4dt03338h

data_7717766
_publ_section_title
;
 Ambient-pressure selective hydrogenation of unsaturated aldehydes and
 ketones into unsaturated alcohols in the water phase.
;
_journal_issue                   5
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1791
_journal_page_last               1796
_journal_paper_doi               10.1039/d4dt03338h
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         '2(C25 H34 Cl2 N3 P Ru), C4 H8 O'
_chemical_formula_sum            'C54 H76 Cl4 N6 O P2 Ru2'
_chemical_formula_weight         1231.08
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2024-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-09-19 deposited with the CCDC.	2025-01-06 downloaded from the CCDC.
;
_cell_angle_alpha                88.336(11)
_cell_angle_beta                 89.350(12)
_cell_angle_gamma                76.815(13)
_cell_formula_units_Z            1
_cell_length_a                   11.2337(17)
_cell_length_b                   11.6564(17)
_cell_length_c                   11.8853(15)
_cell_measurement_reflns_used    2118
_cell_measurement_temperature    125(30)
_cell_measurement_theta_max      69.5710
_cell_measurement_theta_min      4.0280
_cell_volume                     1514.6(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'ShelXS-1997 (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      125(30)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.966
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_details
;
  1 omega  -47.00   30.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672   37.0000  -30.0000 77

  2 omega  -49.00   35.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672   37.0000 -180.0000 84

  3 omega    3.00   41.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5672  -99.0000 -120.0000 38

  4 omega   56.00   98.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       40.5672 -125.0000  -30.0000 42

  5 omega   36.00   84.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  -45.0000 -120.0000 48

  6 omega   50.00  100.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  -94.0000  -90.0000 50

  7 omega   41.00   87.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  -94.0000 -150.0000 46

  8 omega   37.00   89.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  -30.0000 -180.0000 52

  9 omega   23.00  105.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  -94.0000    0.0000 82

 10 omega   36.00   85.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  -45.0000    0.0000 49

 11 omega   27.00   86.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  -30.0000  120.0000 59

 12 omega   77.00  176.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446   30.0000  120.0000 99

 13 omega   95.00  120.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  125.0000  -60.0000 25

 14 omega  109.00  166.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446  125.0000  -90.0000 57

 15 omega   76.00  163.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446   45.0000   30.0000 87

 16 omega   48.00  122.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      103.3446 -125.0000  150.0000 74

 17 omega -115.00  -13.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.5672  -57.0000   30.0000 102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0623741000
_diffrn_orient_matrix_UB_12      -0.0001104000
_diffrn_orient_matrix_UB_13      0.1147857000
_diffrn_orient_matrix_UB_21      -0.0780465000
_diffrn_orient_matrix_UB_22      0.1245589000
_diffrn_orient_matrix_UB_23      0.0208439000
_diffrn_orient_matrix_UB_31      -0.0992863000
_diffrn_orient_matrix_UB_32      -0.0540819000
_diffrn_orient_matrix_UB_33      0.0566179000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1404
_diffrn_reflns_av_unetI/netI     0.2107
_diffrn_reflns_Laue_measured_fraction_full 0.966
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            8644
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        64.983
_diffrn_reflns_theta_max         64.983
_diffrn_reflns_theta_min         3.721
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.468
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68225
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.350
_exptl_crystal_description       needle
_exptl_crystal_F_000             636
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.555
_refine_diff_density_min         -3.344
_refine_diff_density_rms         0.199
_refine_ls_extinction_coef       0.0025(5)
_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   0.979
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         4976
_refine_ls_number_restraints     275
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1771
_refine_ls_R_factor_gt           0.1251
_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^)+(0.1680P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2891
_refine_ls_wR_factor_ref         0.3539
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2326
_reflns_number_total             4976
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03338h2.cif
_cod_data_source_block           12
_cod_depositor_comments
'Adding full bibliography for 7717765--7717767.cif.'
_cod_database_code               7717766
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.32
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C29-C27
 2.5 with sigma of 0.02
 O1-C29
 1.48 with sigma of 0.02
 O1-C29 = O1-C26 = C27-C26 = C28-C27 = C29-C28
 1.48 with sigma of 0.01
 C29-C26
 2.5 with sigma of 0.02
 C29A-C26A
 2.5 with sigma of 0.02
 O1-C26
 1.48 with sigma of 0.01
 O1-C28
 2.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1 \\sim C29 \\sim C27 \\sim C26 \\sim C28 \\sim C29A \\sim O1A \\sim C26A
\\sim C28A \\sim C27A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(O1) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C26)
\\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(O1A) \\sim Ueq,
Uanis(C26A) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C27A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 O1, C29, C27, C26, C28, C29A, O1A, C26A, C28A, C27A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C29A)=Sof(H29C)=Sof(H29D)=Sof(O1A)=Sof(C26A)=Sof(H26C)=Sof(H26D)=
 Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C27A)=Sof(H27C)=Sof(H27D)=0.5*(1-FVAR(2))
 Sof(O1)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C26)=
 Sof(H26A)=Sof(H26B)=Sof(C28)=Sof(H28A)=Sof(H28B)=0.5*FVAR(2)
 Fixed U11: O1(0.070306) C26(0.069135) C29A(0.071207) O1A(0.072208)
 Fixed U12: O1(-0.000042) C26(-0.000324) C29A(0.000962) O1A(0.003801)
 Fixed U13: O1(-0.001271) C26(-0.000717) C29A(-0.002881) O1A(-0.001554)
 Fixed U22: O1(0.070002) C26(0.069615) C29A(0.06978) O1A(0.071611)
 Fixed U23: O1(-0.000498) C26(-0.000261) C29A(-0.001077) O1A(-0.001471)
 Fixed U33: O1(0.07147) C26(0.07028) C29A(0.07228) O1A(0.07067)
 Fixed X: O1(-0.080311) C29(-0.1458) C27(0.018351) C26(-0.012671) C28(-
 0.04823) C29A(-0.101219) O1A(-0.03569) C26A(0.027101) C28A(-0.12415) C27A(-
 0.01988)
 Fixed Y: O1(0.942209) C29(0.839829) C27(0.79933) C26(0.930679) C28(0.72504)
 C29A(0.86005) O1A(0.914209) C26A(0.82442) C28A(0.75596) C27A(0.719729)
 Fixed Z: O1(0.24496) C29(0.26914) C27(0.11485) C26(0.13566) C28(0.207729)
 C29A(0.244049) O1A(0.153901) C26A(0.073509) C28A(0.18686) C27A(0.10847)
6.a Ternary CH refined with riding coordinates:
 N2(H2), N1(H1), N3(H3)
6.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C21(H21A,H21B), C22(H22A,H22B), C24(H24A,H24B), C29(H29A,
 H29B), C27(H27A,H27B), C26(H26A,H26B), C28(H28A,H28B), C29A(H29C,H29D),
 C26A(H26C,H26D), C28A(H28C,H28D), C27A(H27C,H27D)
6.c Me refined with riding coordinates:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
6.d Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C10(H10), C9(H9), C8(H8), C16(H16), C17(H17), C14(H14),
 C15(H15), C3(H3A), C2(H2A), C6(H6), C5(H5), C4(H4)
6.e Fitted hexagon refined as free rotating group:
 C7(C12,C11,C10,C9,C8), C16(C17,C18,C13,C14,C15), C3(C2,C1,C6,C5,C4)
6.f Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
;
_shelx_res_checksum              33880
_olex2_submission_special_instructions 'No special instructions were received'