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_1568891
_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         'C16 H29 N2 Rh'
_chemical_formula_sum            'C16 H29 N2 Rh'
_chemical_formula_weight         352.32
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2f3d65
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.7527(4)
_cell_length_b                   10.0218(3)
_cell_length_c                   30.3983(11)
_cell_measurement_reflns_used    14911
_cell_measurement_temperature    230.00(10)
_cell_measurement_theta_max      79.8400
_cell_measurement_theta_min      2.8370
_cell_volume                     3275.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      230.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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     93.00 169.00   0.50    1.01    --  113.25  77.00  90.00  152
  2  \w    131.00 171.00   0.50    1.01    --  113.25  95.00 127.00   80
  3  \w    104.00 165.00   0.50    1.01    --  113.25  15.00  90.00  122
  4  \w    102.00 178.00   0.50    1.01    --  113.25  45.00 -60.00  152
  5  \w    115.00 141.00   0.50    1.01    --  113.25  45.00-120.00   52
  6  \w    -27.00   2.00   0.50    0.25    --  -47.52  19.00-120.00   58
  7  \w    -50.00 -22.00   0.50    1.01    --  -91.75  45.00 -60.00   56
  8  \w    -47.00 -21.00   0.50    1.01    --  -91.75  45.00 -30.00   52
  9  \w    -66.00   7.00   0.50    0.25    --  -47.52  95.00 127.00  146
 10  \w    -74.00 -49.00   0.50    1.01    --  -91.75  95.00 127.00   50
 11  \w   -147.00-122.00   0.50    1.01    --  -91.75 -95.00  16.00   50
 12  \w   -113.00 -74.00   0.50    0.25    --  -47.52-125.00 150.00   78
 13  \w   -119.00 -73.00   0.50    0.25    --  -47.52-125.00-180.00   92
 14  \w   -113.00 -81.00   0.50    0.25    --  -47.52-125.00-120.00   64
 15  \w     43.00  69.00   0.50    1.01    --  113.25-125.00 150.00   52
 16  \w     85.00 110.00   0.50    1.01    --  113.25-125.00 150.00   50
 17  \w     42.00  67.00   0.50    1.01    --  113.25-125.00  30.00   50
 18  \w     63.00  99.00   0.50    1.01    --  113.25-125.00   0.00   72
 19  \w     42.00  84.00   0.50    1.01    --  113.25 -95.00  30.00   84
 20  \w     61.00  87.00   0.50    1.01    --  113.25 -95.00  16.00   52
 21  \w     42.00 105.00   0.50    1.01    --  113.25 -95.00 120.00  126
 22  \w     -5.00  75.00   0.50    0.25    --   47.52 -95.00  16.00  160
 23  \w     46.00  72.00   0.50    1.01    --  113.25-125.00-120.00   52
 24  \w     46.00  93.00   0.50    1.01    --  113.25 -77.00-150.00   94
 25  \w     42.00  70.00   0.50    1.01    --  113.25 -61.00-120.00   56
 26  \w     45.00  71.00   0.50    1.01    --  113.25 -61.00  30.00   52
 27  \w     58.00  84.00   0.50    1.01    --  113.25 -77.00  60.00   52
 28  \w     45.00  70.00   0.50    1.01    --  113.25 -61.00  90.00   50
 29  \w     42.00  67.00   0.50    1.01    --  113.25 -61.00  60.00   50
 30  \w     42.00  70.00   0.50    1.01    --  113.25 -61.00 -90.00   56
 31  \w     42.00  67.00   0.50    1.01    --  113.25 -61.00-150.00   50
;
_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      -0.1371268000
_diffrn_orient_matrix_UB_12      0.0062808000
_diffrn_orient_matrix_UB_13      -0.0145738000
_diffrn_orient_matrix_UB_21      0.0356700000
_diffrn_orient_matrix_UB_22      -0.0607418000
_diffrn_orient_matrix_UB_23      -0.0448065000
_diffrn_orient_matrix_UB_31      -0.0216139000
_diffrn_orient_matrix_UB_32      -0.1410060000
_diffrn_orient_matrix_UB_33      0.0186639000
_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  0.0468
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            24606
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.135
_diffrn_reflns_theta_min         2.907
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.329
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.37840
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_preparation       'Synthesis from salt metathesis'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Pentane'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.771
_refine_diff_density_min         -1.180
_refine_diff_density_rms         0.082
_refine_ls_extinction_coef       0.00112(7)
_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   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     199
_refine_ls_number_reflns         3541
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0384
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0519P)^2^+3.2090P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1018
_refine_ls_wR_factor_ref         0.1038
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3204
_reflns_number_total             3541
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01163a2.cif
_cod_data_source_block           mc075_auto
_cod_depositor_comments
'Adding full bibliography for 1568890--1568891.cif.'
_cod_database_code               1568891
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Rh N C H'
_chemical_oxdiff_usercomment     '230 K'
_shelx_estimated_absorpt_t_max   0.301
_shelx_estimated_absorpt_t_min   0.240
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 C16A-C14 \\sim C16B-C14 \\sim C15A-C14 \\sim C15B-C14
 with sigma of 0.02
3. Others
 Sof(H14A)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16D)=
 Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(H14)=Sof(C15B)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16B)=Sof(H16A)=
 Sof(H16B)=Sof(H16C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C5(H5), C11(H11), C2(H2), C14(H14), C14(H14A), C1(H1)
4.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C7(H7A,H7B), C3(H3A,H3B), C8(H8A,H8B)
4.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C10(H10A,H10B,H10C), C15B(H15A,H15B,
 H15C), C16B(H16A,H16B,H16C), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F)
;
_shelx_res_checksum              21229
_olex2_date_sample_completion    2022-01-15
_olex2_date_sample_data_collection 2022-11-15
_olex2_date_sample_submission    2022-01-15
_olex2_exptl_crystal_mounting_method 'In perfluorinated oil'
_olex2_submission_original_sample_id MC075
_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 1.778
_oxdiff_exptl_absorpt_empirical_full_min 0.571