Simple NMR predictors of catalytic hydrogenation activity for [Rh(cod)Cl(NHC)] complexes featuring fluorinated NHC ligands.
Jamil, Mohamad Shazwan Shah; Alkaabi, Sultan; Brisdon, Alan K.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 9317–9327; doi:10.1039/c9dt01219b

data_7700126
_publ_section_title
;
 Simple NMR predictors of catalytic hydrogenation activity for
 [Rh(cod)Cl(NHC)] complexes featuring fluorinated NHC ligands.
;
_journal_issue                   25
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9317
_journal_page_last               9327
_journal_paper_doi               10.1039/c9dt01219b
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         '4(C23 H22 Cl F2 N2 Rh)'
_chemical_formula_sum            'C92 H88 Cl4 F8 N8 Rh4'
_chemical_formula_weight         2011.14
_chemical_name_common            Rh(cod)Cl(4-F-IPh)
_chemical_name_systematic
;
 rhodium(cycloocatdienyl)(1,3-bis(4-fluorophenyl)imidazol-2-ylidene)chloride
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-12 deposited with the CCDC.    2019-05-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.479(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.6184(7)
_cell_length_b                   17.4744(8)
_cell_length_c                   17.3930(12)
_cell_measurement_reflns_used    5301
_cell_measurement_temperature    150.0(3)
_cell_measurement_theta_max      26.2830
_cell_measurement_theta_min      3.0010
_cell_volume                     4131.4(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.873
_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    -90.00 -39.00   1.00   26.70    --  -18.77 178.00  90.00   51
  2  \w     41.00  94.00   1.00   26.70    --   20.02 178.00-150.00   53
  3  \w     -5.00  24.00   1.00   26.70    --   20.02  37.00  60.00   29
  4  \w     43.00  90.00   1.00   26.70    --   20.02  37.00  60.00   47
  5  \w     15.00  80.00   1.00   26.70    --   20.02  77.00 -30.00   65
  6  \w     36.00  98.00   1.00   26.70    --   20.02 178.00   0.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0398230000
_diffrn_orient_matrix_UB_12      0.0253141000
_diffrn_orient_matrix_UB_13      -0.0087591000
_diffrn_orient_matrix_UB_21      -0.0191391000
_diffrn_orient_matrix_UB_22      -0.0256721000
_diffrn_orient_matrix_UB_23      -0.0287560000
_diffrn_orient_matrix_UB_31      -0.0278184000
_diffrn_orient_matrix_UB_32      -0.0186148000
_diffrn_orient_matrix_UB_33      0.0276514000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0631
_diffrn_reflns_av_unetI/netI     0.1254
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.873
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            24464
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.873
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.952
_diffrn_reflns_theta_min         2.771
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.985
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60726
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.617
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2032
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.413
_refine_diff_density_min         -0.714
_refine_diff_density_rms         0.138
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.47(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1016
_refine_ls_number_reflns         14705
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1020
_refine_ls_R_factor_gt           0.0748
_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^)+(0.0541P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1413
_refine_ls_wR_factor_ref         0.1580
_reflns_Friedel_coverage         0.938
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.872
_reflns_number_gt                11041
_reflns_number_total             14705
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt01219b2.cif
_cod_data_source_block           aab65
_cod_depositor_comments
'Adding full bibliography for 7700125--7700129.cif.'
_cod_database_code               7700126
_shelxl_version_number           2014-3
_chemical_oxdiff_formula         RhClC23H22F2N2
_chemical_oxdiff_usercomment     STL/LTH
_shelx_estimated_absorpt_t_max   0.952
_shelx_estimated_absorpt_t_min   0.866
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.53(5)
 0.47(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C70) \\sim Ueq, Uanis(C89) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C24) = Uanis(C70)
Uanis(C90) = Uanis(C89) = Uanis(C70)
4. Rigid body (RIGU) restrains
 C56, C57, C58, C59, C60, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C50, C51, C52, C53, C54, C55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C85, C88, C89, C92
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C16(H16), C19(H19), C20(H20), C23(H23), C39(H39), C42(H42), C43(H43),
 C46(H46), C62(H62), C65(H65), C66(H66), C69(H69), C85(H85), C88(H88), C92(H92),
  C89(H89)
5.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C18(H18A,H18B), C21(H21A,H21B), C22(H22A,H22B), C40(H40A,
 H40B), C41(H41A,H41B), C44(H44A,H44B), C45(H45A,H45B), C63(H63A,H63B),
 C64(H64A,H64B), C67(H67A,H67B), C68(H68A,H68B), C86(H86A,H86B), C87(H87A,H87B),
  C90(H90A,H90B), C91(H91A,H91B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14),
 C15(H15), C25(H25), C26(H26), C28(H28), C29(H29), C31(H31), C32(H32), C34(H34),
  C35(H35), C37(H37), C38(H38), C48(H48), C49(H49), C51(H51), C52(H52),
 C54(H54), C55(H55), C57(H57), C58(H58), C60(H60), C61(H61), C71(H71), C72(H72),
  C74(H74), C75(H75), C77(H77), C78(H78), C84(H84), C80(H80), C81(H81), C83(H83)
5.d Fitted hexagon refined as free rotating group:
 C84(C79,C80,C81,C82,C83)
;
_shelx_res_checksum              88433
_olex2_date_sample_data_collection 2018-02-09
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.067
_oxdiff_exptl_absorpt_empirical_full_min 0.652