The promotional role of Mn in CO<sub>2</sub> hydrogenation over Rh-based catalysts from a surface organometallic chemistry approach.
Zhou, Wei; Docherty, Scott R.; Ehinger, Christian; Zhou, Xiaoyu; Copéret, Christophe; Chemical science 14 (2023) 5379–5385; doi:10.1039/d3sc01163a

data_1568890
_publ_section_title
;
 The promotional role of Mn in CO<sub>2</sub> hydrogenation over Rh-based
 catalysts from a surface organometallic chemistry approach.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              5379
_journal_page_last               5385
_journal_paper_doi               10.1039/d3sc01163a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         '0.5(C24 H50 Li2 N4 O2)'
_chemical_formula_sum            'C12 H25 Li N2 O'
_chemical_formula_weight         220.28
_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     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2f3d76
_audit_creation_date             2023-01-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-01-23 deposited with the CCDC.	2023-04-14 downloaded from the CCDC.
;
_cell_angle_alpha                91.735(3)
_cell_angle_beta                 97.167(3)
_cell_angle_gamma                101.208(3)
_cell_formula_units_Z            4
_cell_length_a                   9.5447(3)
_cell_length_b                   10.6072(3)
_cell_length_c                   14.7411(5)
_cell_measurement_reflns_used    10092
_cell_measurement_temperature    232.99(10)
_cell_measurement_theta_max      79.9370
_cell_measurement_theta_min      2.9690
_cell_volume                     1450.24(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.61a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.61a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.61a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      232.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.970
_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    -78.00  17.00   0.50    0.96    --  -49.62  96.00  36.00  190
  2  \w      3.00  50.00   0.50    0.96    --   49.62 -96.00 -72.00   94
  3  \w    -74.00 -49.00   0.50    3.84    --  -90.00  96.00  36.00   50
  4  \w   -119.00 -86.00   0.50    3.84    --  -90.00 -96.00 -72.00   66
  5  \w    137.00 163.00   0.50    3.84    --  111.50  96.00  36.00   52
  6  \w     67.00 105.00   0.50    3.84    --  111.50 -96.00 -72.00   76
  7  \w   -114.00 -74.00   0.50    0.96    --  -49.62-125.00  90.00   80
  8  \w   -108.00 -75.00   0.50    0.96    --  -49.62-125.00 -30.00   66
  9  \w    -23.00   6.00   0.50    0.96    --  -49.62  19.00 120.00   58
 10  \w    -24.00  23.00   0.50    0.96    --  -49.62  19.00-150.00   94
 11  \w     -9.00  22.00   0.50    0.96    --  -49.62  38.00 -30.00   62
 12  \w    -42.00 -11.00   0.50    0.96    --  -49.62  38.00 -30.00   62
 13  \w    -17.00  37.00   0.50    0.96    --   49.62 -38.00   0.00  108
 14  \w   -159.00-133.00   0.50    3.84    --  -90.00 -95.00  30.00   52
 15  \w   -127.00 -97.00   0.50    3.84    --  -90.00 -95.00  30.00   60
 16  \w     43.00  68.00   0.50    3.84    --  111.50 -61.00   0.00   50
 17  \w    133.00 160.00   0.50    3.84    --  111.50  30.00 -30.00   54
 18  \w     77.00 103.00   0.50    3.84    --  111.50 -95.00-120.00   52
 19  \w    107.00 178.00   0.50    3.84    --  111.50  30.00 -60.00  142
 20  \w     76.00 105.00   0.50    3.84    --  111.50 -95.00 -30.00   58
 21  \w     41.00  66.00   0.50    3.84    --  111.50 -61.00 -60.00   50
 22  \w     47.00  75.00   0.50    3.84    --  111.50 -77.00  90.00   56
 23  \w     42.00  72.00   0.50    3.84    --  111.50 -95.00-120.00   60
 24  \w     42.00  68.00   0.50    3.84    --  111.50 -61.00 -30.00   52
 25  \w     91.00 127.00   0.50    3.84    --  111.50  77.00-150.00   72
 26  \w     76.00 105.00   0.50    3.84    --  111.50 -95.00  60.00   58
 27  \w    130.00 177.00   0.50    3.84    --  111.50  30.00-120.00   94
 28  \w     63.00 105.00   0.50    3.84    --  111.50 -95.00  30.00   84
 29  \w     44.00 104.00   0.50    3.84    --  111.50 -99.00 154.91  120
 30  \w     51.00  85.00   0.50    3.84    --  111.50 -77.00-180.00   68
 31  \w     51.00 111.00   0.50    3.84    --  111.50-125.00-120.00  120
 32  \w     45.00  71.00   0.50    3.84    --  111.50 -83.00 -73.65   52
 33  \w     93.00 119.00   0.50    3.84    --  111.50 -83.00 -73.65   52
 34  \w     41.00  66.00   0.50    3.84    --  111.50 -61.00-120.00   50
 35  \w    103.00 140.00   0.50    3.84    --  111.50  45.00-150.00   74
 36  \w    153.00 178.00   0.50    3.84    --  111.50  45.00-150.00   50
 37  \w    116.00 169.00   0.50    3.84    --  111.50  45.00   0.00  106
 38  \w     80.00 105.00   0.50    3.84    --  111.50 -95.00 -90.00   50
 39  \w     41.00  68.00   0.50    3.84    --  111.50 -95.00 -90.00   54
 40  \w     42.00  74.00   0.50    3.84    --  111.50 -77.00  60.00   64
 41  \w     42.00  83.00   0.50    3.84    --  111.50 -95.00  90.00   82
 42  \w     42.00  67.00   0.50    3.84    --  111.50 -95.00  60.00   50
 43  \w    123.00 150.00   0.50    3.84    --  111.50  45.00-180.00   54
 44  \w    134.00 160.00   0.50    3.84    --  111.50  30.00  30.00   52
 45  \w    152.00 177.00   0.50    3.84    --  111.50  15.00-150.00   50
 46  \w    153.00 178.00   0.50    3.84    --  111.50  77.00-150.00   50
 47  \w     41.00  66.00   0.50    3.84    --  111.50 -61.00 -90.00   50
 48  \w     43.00  68.00   0.50    3.84    --  111.50 -77.00 -30.00   50
 49  \w     69.00 100.00   0.50    3.84    --  111.50 -95.00   0.00   62
 50  \w     48.00 101.00   0.50    3.84    --  111.50 -95.00 120.00  106
 51  \w    106.00 136.00   0.50    3.84    --  111.50  15.00 150.00   60
 52  \w    136.00 162.00   0.50    3.84    --  111.50 125.00  60.00   52
 53  \w     92.00 122.00   0.50    3.84    --  111.50  77.00  90.00   60
 54  \w    153.00 178.00   0.50    3.84    --  111.50  77.00  90.00   50
 55  \w     92.00 135.00   0.50    3.84    --  111.50  77.00 120.00   86
 56  \w     45.00  70.00   0.50    3.84    --  111.50 -77.00   0.00   50
 57  \w     57.00 104.00   0.50    3.84    --  111.50 -95.00-180.00   94
 58  \w     85.00 111.00   0.50    3.84    --  111.50-125.00 -90.00   52
 59  \w     84.00 111.00   0.50    3.84    --  111.50-125.00 150.00   54
 60  \w    113.00 139.00   0.50    3.84    --  111.50  30.00-180.00   52
 61  \w    153.00 178.00   0.50    3.84    --  111.50 125.00  30.00   50
 62  \w     94.00 176.00   0.50    3.84    --  111.50  77.00 150.00  164
 63  \w    122.00 169.00   0.50    3.84    --  111.50  15.00 120.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0799462000
_diffrn_orient_matrix_UB_12      0.0212201000
_diffrn_orient_matrix_UB_13      -0.0939609000
_diffrn_orient_matrix_UB_21      -0.1434376000
_diffrn_orient_matrix_UB_22      -0.0682768000
_diffrn_orient_matrix_UB_23      0.0296735000
_diffrn_orient_matrix_UB_31      -0.0244591000
_diffrn_orient_matrix_UB_32      0.1299204000
_diffrn_orient_matrix_UB_33      0.0376868000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0204
_diffrn_reflns_av_unetI/netI     0.0237
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            21990
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.297
_diffrn_reflns_theta_min         3.026
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.483
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97271
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.61a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.009
_exptl_crystal_description       block
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.468
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     328
_refine_ls_number_reflns         6163
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0740
_refine_ls_R_factor_gt           0.0663
_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^)+(0.1109P)^2^+0.3008P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2008
_refine_ls_wR_factor_ref         0.2093
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5264
_reflns_number_total             6163
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01163a2.cif
_cod_data_source_block           exp_1946_auto
_cod_depositor_comments
'Adding full bibliography for 1568890--1568891.cif.'
_cod_database_code               1568890
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         LiC12H25N2O
_chemical_oxdiff_usercomment     '-40 C'
_shelx_estimated_absorpt_t_max   0.918
_shelx_estimated_absorpt_t_min   0.893
_reflns_odcompleteness_completeness 96.22
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_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
 C25-C26 \\sim C31-C32
 with sigma of 0.02
 C14-C15 \\sim C11-C10
 with sigma of 0.02
 O3-C25 \\sim O3-C32
 with sigma of 0.02
 O1-C12 \\sim O2-C16
 with sigma of 0.02
 C11-C12 \\sim C16-C15
 with sigma of 0.02
 O3-C28 \\sim O3-C29
 with sigma of 0.02
 O3-C29 \\sim O3-C28
 with sigma of 0.02
 O1-C9 \\sim O2-C13
 with sigma of 0.02
 C13-C14 \\sim C10-C9
 with sigma of 0.02
 C26-C27 \\sim C30-C31
 with sigma of 0.02
 C28-C27 \\sim C30-C29
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C9) = Uanis(C13)
Uanis(C32) = Uanis(C25)
Uanis(C27) = Uanis(C30)
Uanis(C14) = Uanis(C10)
Uanis(C29) = Uanis(C28)
Uanis(C11) = Uanis(C15)
Uanis(C31) = Uanis(C26)
Uanis(C12) = Uanis(C16)
Uanis(O1) = Uanis(O2)
4. Others
 Sof(C28)=Sof(H17A)=Sof(H17B)=Sof(C27)=Sof(H00Z)=Sof(H)=Sof(C26)=Sof(H18A)=
 Sof(H18B)=Sof(C25)=Sof(H19A)=Sof(H19B)=1-FVAR(1)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(C30)=Sof(H30A)=Sof(H30B)=FVAR(1)
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(O2)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(C15)=Sof(H15A)=Sof(H15B)=1-FVAR(2)
 Sof(O1)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=
 Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11A)=Sof(H11B)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C6(H6), C3(H3), C22(H22), C19(H19)
5.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C9(H9A,H9B), C32(H32A,H32B), C10(H10A,H10B), C29(H29A,H29B),
 C31(H31A,H31B), C11(H11A,H11B), C30(H30A,H30B), C28(H17A,H17B), C27(H00Z,H),
 C26(H18A,H18B), C25(H19A,H19B), C14(H14A,H14B), C13(H13A,H13B), C16(H16A,H16B),
  C15(H15A,H15B)
5.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C18(H18C,H18D,H18E), C8(H8A,H8B,H8C), C7(H7A,H7B,H7C),
 C24(H24A,H24B,H24C), C4(H4A,H4B,H4C), C21(H21A,H21B,H21C), C5(H5A,H5B,H5C),
 C23(H23A,H23B,H23C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              60275
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.223
_oxdiff_exptl_absorpt_empirical_full_min 0.880