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_4517329
_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         'C32 H12 B F24, C24 H44 F2 P2 Rh'
_chemical_formula_sum            'C56 H56 B F26 P2 Rh'
_chemical_formula_weight         1398.66
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-17
_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            8
_cell_length_a                   35.5500(5)
_cell_length_b                   17.7103(2)
_cell_length_c                   18.7565(3)
_cell_measurement_reflns_used    16333
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      75.6390
_cell_measurement_theta_min      2.7820
_cell_volume                     11809.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31c (Rigaku OD, 2017)'
_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      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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      6.00  51.00   1.00    2.00    --    0.00 -99.00-180.00   45
  2  \w      6.00  33.00   1.00    2.00    --    0.00 -99.00-120.00   27
  3  \w    -99.00 -41.00   1.00    2.00    --    0.00 178.00-150.00   58
  4  \w    -46.00  10.00   1.00    6.00    --  -59.95  30.00 -90.00   56
  5  \w   -133.00 -81.00   1.00    6.00    --  -59.95 -94.00 -60.00   52
  6  \w    -34.00  17.00   1.00    6.00    --  -59.95  30.00   0.00   51
  7  \w    -56.00  25.00   1.00    6.00    --  -59.95  45.00-180.00   81
  8  \w   -150.00 -83.00   1.00    6.00    --  -59.95 -94.00 150.00   67
  9  \w   -132.00 -97.00   1.00    6.00    --  -59.95 -94.00-120.00   35
 10  \w    102.00 127.00   1.00    6.00    --   59.95 121.00-122.00   25
 11  \w     32.00  91.00   1.00   15.00    --  119.91 -37.00  90.00   59
 12  \w     34.00 105.00   1.00   15.00    --  119.91 -50.00  30.00   71
 13  \w     37.00  91.00   1.00   15.00    --  119.91 -37.00-150.00   54
 14  \w    129.00 168.00   1.00   15.00    --  119.91 111.00 -30.00   39
 15  \w     62.00  89.00   1.00   15.00    --  119.91 -37.00 150.00   27
 16  \w     61.00  92.00   1.00   15.00    --  119.91 -37.00-120.00   31
 17  \w     43.00  80.00   1.00   15.00    --  119.91 -25.00  30.00   37
 18  \w     32.00  69.00   1.00   15.00    --  119.91 -37.00 -60.00   37
 19  \w     20.00 170.00   1.00   15.00    --  119.91   0.00  30.00  150
 20  \w    -98.00 -71.00   1.00    2.00    --    0.00 178.00   0.00   27
 21  \w     25.00  51.00   1.00    2.00    --    0.00 -99.00-150.00   26
 22  \w     10.00  50.00   1.00    2.00    --    0.00 -99.00 150.00   40
 23  \w    -66.00 -39.00   1.00    2.00    --    0.00 178.00   0.00   27
 24  \w    -61.00 -55.00   1.00    6.00    --  -59.95 -45.00 120.00    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      0.0223539000
_diffrn_orient_matrix_UB_12      -0.0115974000
_diffrn_orient_matrix_UB_13      0.0414352000
_diffrn_orient_matrix_UB_21      -0.0520114000
_diffrn_orient_matrix_UB_22      0.0619698000
_diffrn_orient_matrix_UB_23      0.0117613000
_diffrn_orient_matrix_UB_31      -0.0660358000
_diffrn_orient_matrix_UB_32      -0.0526540000
_diffrn_orient_matrix_UB_33      0.0047699000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            46114
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.043
_diffrn_reflns_theta_min         2.788
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.937
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89458
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'yellowish orange'
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.573
_exptl_crystal_description       plate
_exptl_crystal_F_000             5648
_exptl_crystal_size_max          0.162
_exptl_crystal_size_mid          0.159
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.449
_refine_diff_density_min         -1.249
_refine_diff_density_rms         0.113
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1161
_refine_ls_number_reflns         12210
_refine_ls_number_restraints     1749
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.1167
_refine_ls_R_factor_gt           0.1069
_refine_ls_shift/su_max          0.019
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1217P)^2^+72.9986P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2780
_refine_ls_wR_factor_ref         0.2856
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10373
_reflns_number_total             12210
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b03727_si_002.cif
_cod_data_source_block           9
_cod_depositor_comments
'Adding full bibliography for 4517328--4517333.cif.'
_cod_database_code               4517329
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H66 P2 Rh1 B1 F24'
_shelx_estimated_absorpt_t_max   0.718
_shelx_estimated_absorpt_t_min   0.568
_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
 F8-F7 \\sim F8A-F7A
 with sigma of 0.04
 C32-F8 \\sim C32-F8A \\sim C32-F6A \\sim C32-F6 \\sim C32-F7A \\sim C32-F7
 with sigma of 0.02
 F25-F26 \\sim F25-F24 \\sim F26-F24 \\sim F25A-F26A \\sim F25A-F24A \\sim
F26A-F24A
 with sigma of 0.04
 C56-F25 \\sim C56-F26 \\sim C56-F24 \\sim C56-F25A \\sim C56-F26A \\sim
C56-F24A
 with sigma of 0.02
 F18-F20 \\sim F18-F19 \\sim F20-F19 \\sim F18A-F19A \\sim F18A-F20A \\sim
F19A-F20A
 with sigma of 0.04
 C48-F18 \\sim C48-F20 \\sim C48-F19 \\sim C48-F18A \\sim C48-F19A \\sim
C48-F20A
 with sigma of 0.02
 Rh1-P1 \\sim Rh1-P2
 with sigma of 0.01
 F1-C2 \\sim F2-C1
 with sigma of 0.02
 C13A-C14A \\sim C13A-C16A \\sim C13A-C15A
 with sigma of 0.02
 C14A-C15A \\sim C15A-C16A \\sim C16A-C14A
 with sigma of 0.01
 C9A-C12A \\sim C9A-C11A \\sim C9A-C10A
 with sigma of 0.02
 C17A-C20A \\sim C17A-C19A \\sim C17A-C18A
 with sigma of 0.02
 C21A-C22A \\sim C21A-C23A \\sim C21A-C24A
 with sigma of 0.02
 F13-F12 \\sim F13-F14 \\sim F12-F14 \\sim F13A-F12A \\sim F13A-F14A \\sim
F12A-F14A
 with sigma of 0.04
 C40-F13 \\sim C40-F12 \\sim C40-F14 \\sim C40-F13A \\sim C40-F12A \\sim
C40-F14A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C32 \\sim F6 \\sim F7 \\sim F8 \\sim F6A \\sim F7A \\sim F8A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C56 \\sim F24 \\sim F25 \\sim F26 \\sim F24A \\sim F25A \\sim F26A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C48 \\sim F18 \\sim F19 \\sim F20 \\sim F18A \\sim F19A \\sim F20A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
Rh1 \\sim P1 \\sim P2 \\sim F1 \\sim F2 \\sim C1 \\sim C3 \\sim C4 \\sim C5
\\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13
\\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21
\\sim C22 \\sim C23 \\sim C24: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01
Rh1 \\sim P1 \\sim P2 \\sim F1 \\sim F2 \\sim C1 \\sim C2 \\sim C3 \\sim C4
\\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12
\\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20
\\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim Rh1A \\sim P1A \\sim P2A \\sim
F1A \\sim F2A \\sim C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim
C7A \\sim C8A \\sim C9A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A
\\sim C15A \\sim C16A \\sim C17A \\sim C18A \\sim C19A \\sim C20A \\sim C21A
\\sim C22A \\sim C23A \\sim C24A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.01
C40 \\sim F12 \\sim F13 \\sim F14 \\sim F12A \\sim F13A \\sim F14A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C32) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C56) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C32, F6, F7, F8, F6A, F7A, F8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C56, F24, F25, F26, F24A, F25A, F26A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C48, F18, F19, F20, F18A, F19A, F20A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Rh1, P1, P2, F1, F2, C1, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14,
 C15, C16, C17, C18, C19, C20, C21, C22, C23, C24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Rh1, P1, P2, F1, F2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13,
 C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, Rh1A, P1A, P2A, F1A,
 F2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A,
  C15A, C16A, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, F12, F13, F14, F12A, F13A, F14A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F6A)=Sof(F7A)=Sof(F8A)=1-FVAR(1)
 Sof(F6)=Sof(F7)=Sof(F8)=FVAR(1)
 Sof(F24A)=Sof(F25A)=Sof(F26A)=1-FVAR(2)
 Sof(F24)=Sof(F25)=Sof(F26)=FVAR(2)
 Sof(F18A)=Sof(F19A)=Sof(F20A)=1-FVAR(3)
 Sof(F18)=Sof(F19)=Sof(F20)=FVAR(3)
 Sof(Rh1A)=Sof(P1A)=Sof(P2A)=Sof(F1A)=Sof(F2A)=Sof(C1A)=Sof(C2A)=Sof(C3A)=
 Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=
 Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(C10A)=Sof(H10D)=
 Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12A)=
 Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16D)=
 Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=
 Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=
 Sof(H20F)=Sof(C21A)=Sof(C22A)=Sof(H22F)=Sof(H22D)=Sof(H22E)=Sof(C23A)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(4)
 Sof(Rh1)=Sof(P1)=Sof(P2)=Sof(F1)=Sof(F2)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=
 Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C13)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(H15C)=Sof(C16)=Sof(H16C)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(C18)=Sof(H18A)=
 Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=
 Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23)=
 Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(4)
 Sof(F12A)=Sof(F13A)=Sof(F14A)=1-FVAR(5)
 Sof(F12)=Sof(F13)=Sof(F14)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C7A(H7AA,H7AB), C8A(H8AA,H8AB)
6.b Me refined with riding coordinates:
 C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F), C12A(H12D,H12E,H12F), C14A(H14D,
 H14E,H14F), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C18A(H18D,H18E,H18F),
 C19A(H19D,H19E,H19F), C20A(H20D,H20E,H20F), C22A(H22F,H22D,H22E), C23A(H23D,
 H23E,H23F), C24A(H24D,H24E,H24F)
6.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C28(H28), C30(H30), C34(H34), C36(H36), C38(H38), C42(H42),
 C44(H44), C46(H46), C50(H50), C52(H52), C54(H54), C3(H3), C4(H4), C5(H5),
 C6(H6), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A)
6.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C14(H14A,H14B,
 H14C), C15(H15A,H15B,H15C), C16(H16C,H16A,H16B), C18(H18A,H18B,H18C), C19(H19A,
 H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C),
 C24(H24A,H24B,H24C)
;
_shelx_res_checksum              80541
_shelx_hkl_checksum              44581
_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 1.370
_oxdiff_exptl_absorpt_empirical_full_min 0.798