Solid‒State Molecular Organometallic Catalysis in Gas/Solid Flow (Flow-SMOM) as Demonstrated by Efficient Room Temperature and Pressure 1-Butene Isomerization
Martínez-Martínez, Antonio J.; Royle, Cameron G.; Furfari, Samantha K.; Suriye, Kongkiat; Weller, Andrew S.; ACS Catalysis  (2020) 1984–1992; doi:10.1021/acscatal.9b03727

data_4517332
_publ_section_title
;
 Solid--State Molecular Organometallic Catalysis in Gas/Solid Flow
 (Flow-SMOM) as Demonstrated by Efficient Room Temperature and Pressure
 1-Butene Isomerization
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1984
_journal_page_last               1992
_journal_paper_doi               10.1021/acscatal.9b03727
_journal_year                    2020
_chemical_formula_moiety         'C37 H82 Cl2 P4 Rh2, 2(C32 H12 B F24)'
_chemical_formula_sum            'C101 H106 B2 Cl2 F48 P4 Rh2'
_chemical_formula_weight         2654.07
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_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)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   24.0564(2)
_cell_length_b                   18.6694(2)
_cell_length_c                   12.35080(10)
_cell_measurement_reflns_used    22512
_cell_measurement_temperature    150.00(13)
_cell_measurement_theta_max      75.9290
_cell_measurement_theta_min      3.6310
_cell_volume                     5546.97(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      150.00(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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      0.00  26.00   1.00    5.00    --  -42.66  38.00  30.00   26
  2  \w    -33.00  29.00   1.00    5.00    --  -42.66  38.00   0.00   62
  3  \w     58.00  96.00   1.00    5.00    --   42.66 178.00-120.00   38
  4  \w     65.00 112.00   1.00    5.00    --   42.66-178.00  30.00   47
  5  \w    104.00 175.00   1.00   20.00    --  111.00  45.00-120.00   71
  6  \w     36.00  61.00   1.00   20.00    --  111.00 -30.00   0.00   25
  7  \w     78.00 107.00   1.00   20.00    --  111.00 -95.00-180.00   29
  8  \w     44.00  94.00   1.00   20.00    --  111.00 -45.00   0.00   50
  9  \w     68.00  95.00   1.00   20.00    --  111.00 -45.00 150.00   27
 10  \w     44.00  90.00   1.00   20.00    --  111.00 -30.00 -60.00   46
 11  \w     86.00 147.00   1.00   20.00    --  111.00 -15.00  60.00   61
 12  \w     64.00 101.00   1.00   20.00    --  111.00 -95.00 150.00   37
 13  \w     31.00  84.00   1.00   20.00    --  111.00 -15.00  60.00   53
 14  \w    -49.00 -22.00   1.00    5.00    --  -42.66  38.00-120.00   27
 15  \w      5.00  30.00   1.00    5.00    --  -42.66  38.00-120.00   25
 16  \w     56.00 126.00   1.00    5.00    --   42.66-178.00-180.00   70
 17  \w     98.00 144.00   1.00   20.00    --  111.00 125.00   0.00   46
 18  \w    147.00 173.00   1.00   20.00    --  111.00  77.00-180.00   26
 19  \w     91.00 117.00   1.00   20.00    --  111.00  77.00-180.00   26
 20  \w    137.00 163.00   1.00   20.00    --  111.00  94.00  -4.00   26
 21  \w     91.00 139.00   1.00   20.00    --  111.00  77.00  60.00   48
 22  \w     67.00 110.00   1.00   20.00    --  111.00 -61.00 120.00   43
 23  \w     96.00 140.00   1.00   20.00    --  111.00  45.00  60.00   44
 24  \w     96.00 124.00   1.00   20.00    --  111.00   0.00   0.00   28
 25  \w    -32.00   9.00   1.00    5.00    --  -42.66  38.00 -30.00   41
 26  \w     75.00 129.00   1.00    5.00    --   42.66 178.00 -60.00   54
 27  \w     58.00  84.00   1.00   20.00    --  111.00 -30.00  90.00   26
 28  \w     62.00  88.00   1.00   20.00    --  111.00 -45.00-180.00   26
 29  \w     84.00 132.00   1.00   20.00    --  111.00 -77.00 -30.00   48
 30  \w     88.00 119.00   1.00   20.00    --  111.00  45.00-150.00   31
 31  \w    101.00 127.00   1.00   20.00    --  111.00 125.00-120.00   26
 32  \w    123.00 150.00   1.00   20.00    --  111.00  45.00-150.00   27
 33  \w     40.00  86.00   1.00   20.00    --  111.00 -30.00-150.00   46
 34  \w     47.00  78.00   1.00   20.00    --  111.00 -61.00  90.00   31
 35  \w   -111.00 -65.00   1.00    5.00    --  -42.66 -57.00 -30.00   46
 36  \w    -38.00   3.00   1.00    5.00    --  -42.66  38.00-180.00   41
 37  \w     -3.00  30.00   1.00    5.00    --  -42.66  38.00 -90.00   33
 38  \w    -46.00 -11.00   1.00    5.00    --  -42.66  38.00 -90.00   35
 39  \w   -114.00 -58.00   1.00    5.00    --  -42.66 -38.00   0.00   56
 40  \w    151.00 176.00   1.00   20.00    --  111.00  45.00  30.00   25
 41  \w     38.00  64.00   1.00   20.00    --  111.00 -30.00 150.00   26
 42  \w     87.00 123.00   1.00   20.00    --  111.00  45.00  30.00   36
 43  \w    141.00 147.00   1.00   20.00    --  111.00 125.00  30.00    6
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0297440000
_diffrn_orient_matrix_UB_12      -0.0667652000
_diffrn_orient_matrix_UB_13      0.0448448000
_diffrn_orient_matrix_UB_21      -0.0515608000
_diffrn_orient_matrix_UB_22      -0.0179471000
_diffrn_orient_matrix_UB_23      0.0688936000
_diffrn_orient_matrix_UB_31      -0.0236141000
_diffrn_orient_matrix_UB_32      -0.0450824000
_diffrn_orient_matrix_UB_33      -0.0937857000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0493
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            55933
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.257
_diffrn_reflns_theta_min         3.579
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.534
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82233
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.589
_exptl_crystal_description       trapezoid
_exptl_crystal_F_000             2676
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.878
_refine_diff_density_min         -0.906
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 4565 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.058(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     869
_refine_ls_number_reflns         11519
_refine_ls_number_restraints     667
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0477
_refine_ls_R_factor_gt           0.0441
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0578P)^2^+8.4012P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1100
_refine_ls_wR_factor_ref         0.1130
_reflns_Friedel_coverage         0.806
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                10839
_reflns_number_total             11519
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03727_si_002.cif
_cod_data_source_block           13
_cod_depositor_comments
'Adding full bibliography for 4517328--4517333.cif.'
_cod_database_code               4517332
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C54 H66 Rh1 P2 B1 F24'
_shelx_estimated_absorpt_t_max   0.713
_shelx_estimated_absorpt_t_min   0.569
_reflns_odcompleteness_completeness 99.89
_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
 F21A-F23A \\sim F21A-F22A \\sim F21-F23 \\sim F21-F22 \\sim F23A-F22A \\sim
F23-F22
 with sigma of 0.04
 F19-F20 \\sim F19-F028 \\sim F20-F028 \\sim F19A-F20A \\sim F19A-F0 \\sim
F20A-F0
 with sigma of 0.04
 F15-F14 \\sim F15-F13 \\sim F14-F13 \\sim F15A-F14A \\sim F15A-F13A \\sim
F14A-F13A
 with sigma of 0.04
 C51-F21A \\sim C51-F21 \\sim C51-F23A \\sim C51-F23 \\sim C51-F22 \\sim
C51-F22A
 with sigma of 0.02
 C50-F19 \\sim C50-F20 \\sim C50-F028 \\sim C50-F19A \\sim C50-F20A
 with sigma of 0.02
 C42-F15 \\sim C42-F14 \\sim C42-F13 \\sim C42-F15A \\sim C42-F14A \\sim
C42-F13A
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F1A-F2A \\sim F1A-F3A \\sim F2A-F3A
 with sigma of 0.04
 F4-F6 \\sim F4-F5 \\sim F6-F5 \\sim F4A-F6A \\sim F4A-F5A \\sim F6A-F5A
 with sigma of 0.04
 C26-F1 \\sim C26-F2 \\sim C26-F3 \\sim C26-F1A \\sim C26-F2A \\sim C26-F3A
 with sigma of 0.02
 C27-F4 \\sim C27-F6 \\sim C27-F5 \\sim C27-F4A \\sim C27-F6A \\sim C27-F5A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C51 \\sim F21 \\sim F22 \\sim F23 \\sim F21A \\sim F22A \\sim F23A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C50 \\sim F19 \\sim F20 \\sim F028 \\sim F0 \\sim F19A \\sim F20A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C42 \\sim F13 \\sim F14 \\sim F15 \\sim F13A \\sim F14A \\sim F15A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C26 \\sim F1 \\sim F2 \\sim F3 \\sim F1A \\sim F2A \\sim F3A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C27 \\sim F4 \\sim F5 \\sim F6 \\sim F4A \\sim F5A \\sim F6A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C51, F21, F22, F23, F21A, F22A, F23A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C50, F19, F20, F028, F0, F19A, F20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C42, F13, F14, F15, F13A, F14A, F15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, F1, F2, F3, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, F4, F5, F6, F4A, F5A, F6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F21A)=Sof(F22A)=Sof(F23A)=1-FVAR(1)
 Sof(F21)=Sof(F22)=Sof(F23)=FVAR(1)
 Sof(F0)=Sof(F19A)=Sof(F20A)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F028)=FVAR(2)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(3)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(3)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(4)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(4)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(5)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(5)
 Fixed Sof: H1A(0.5) H1B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B)
6.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C23(H23), C25(H25), C29(H29), C31(H31), C33(H33), C37(H37),
 C39(H39), C41(H41), C45(H45), C47(H47), C49(H49)
6.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C)
;
_shelx_res_checksum              6293
_shelx_hkl_checksum              94461
_olex2_date_sample_data_collection 2019-03-05
_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 1.264
_oxdiff_exptl_absorpt_empirical_full_min 0.787