Room Temperature Acceptorless Alkane Dehydrogenation from Molecular σ-Alkane Complexes.
McKay, Alasdair I.; Bukvic, Alexander J.; Tegner, Bengt E.; Burnage, Arron L.; Martı Nez-Martı Nez, Antonio J; Rees, Nicholas H.; Macgregor, Stuart A.; Weller, Andrew S.; Journal of the American Chemical Society 141 (2019) 11700–11712; doi:10.1021/jacs.9b05577

data_4127375
_publ_section_title
;
 Room Temperature Acceptorless Alkane Dehydrogenation from Molecular
 \s-Alkane Complexes.
;
_journal_issue                   29
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11700
_journal_page_last               11712
_journal_paper_doi               10.1021/jacs.9b05577
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C32 H56 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C64 H68 B F24 P2 Rh'
_chemical_formula_weight         1468.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.1490(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.2893(2)
_cell_length_b                   17.28280(10)
_cell_length_c                   20.26220(10)
_cell_measurement_reflns_used    18660
_cell_measurement_temperature    249.99(10)
_cell_measurement_theta_max      70.0560
_cell_measurement_theta_min      3.4090
_cell_volume                     6753.51(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (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    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      249.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.987
_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    -84.00  94.00   0.50    1.25    --    5.00  47.00  80.00  356
  2  \w    -89.00  89.00   0.50    1.25    --    0.00   0.00 -30.00  356
  3  \w   -179.00  -1.00   0.50    5.00    --  -90.00  30.00 -30.00  356
  4  \w   -179.00  -1.00   0.50    5.00    --  -90.00  30.00  60.00  356
  5  \w   -179.00 -28.00   0.50    5.00    --  -90.00  39.00 150.00  302
  6  \w   -111.00 -61.00   0.50    5.00    --  -90.00  30.00 -30.00  100
  7  \w   -126.00-100.00   0.50    5.00    --  -90.00  30.00   0.00   52
  8  \w    -90.00 -58.00   0.50    5.00    --  -90.00  30.00   0.00   64
  9  \w    -26.00  -1.00   0.50    5.00    --  -90.00  30.00   0.00   50
 10  \w   -178.00 -60.00   0.50    5.00    --  -90.00  39.00-120.00  236
 11  \w   -179.00  -1.00   0.50    5.00    --  -90.00  47.00  80.00  356
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0510552000
_diffrn_orient_matrix_UB_12      -0.0643871000
_diffrn_orient_matrix_UB_13      -0.0191605000
_diffrn_orient_matrix_UB_21      -0.0211454000
_diffrn_orient_matrix_UB_22      0.0104301000
_diffrn_orient_matrix_UB_23      -0.0731943000
_diffrn_orient_matrix_UB_31      0.0576880000
_diffrn_orient_matrix_UB_32      0.0607326000
_diffrn_orient_matrix_UB_33      -0.0077542000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0349
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            32330
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.054
_diffrn_reflns_theta_min         3.434
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.426
_exptl_absorpt_correction_T_max  0.997
_exptl_absorpt_correction_T_min  0.642
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_description       block
_exptl_crystal_F_000             2992
_exptl_crystal_size_max          0.181
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.072
_refine_diff_density_max         0.973
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     555
_refine_ls_number_reflns         6335
_refine_ls_number_restraints     192
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0597
_refine_ls_R_factor_gt           0.0548
_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^)+(0.1085P)^2^+3.8062P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1653
_refine_ls_wR_factor_ref         0.1709
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5469
_reflns_number_total             6335
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05577_si_002.cif
_cod_data_source_block           1-C6H8
_cod_original_cell_volume        6753.52(9)
_cod_database_code               4127375
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C64 H66 B4 F24 P2 Rh '
_chemical_oxdiff_usercomment     250K
_reflns_odcompleteness_completeness 98.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F8A-C34 \\sim F8B-C34
 with sigma of 0.02
 C34-F9A \\sim C34-F9B
 with sigma of 0.02
 C34-F7A \\sim C34-F7B
 with sigma of 0.02
 F1A-C26 \\sim F3B-C26
 with sigma of 0.02
 F2A-C26 \\sim F1B-C26
 with sigma of 0.02
 F3A-C26 \\sim F2B-C26
 with sigma of 0.02
 F5A-C27 \\sim F4B-C27
 with sigma of 0.02
 F4A-C27 \\sim F6B-C27
 with sigma of 0.02
 C27-F6A \\sim C27-F5B
 with sigma of 0.02
 F12A-C35 \\sim F11B-C35
 with sigma of 0.02
 F10A-C35 \\sim F12B-C35
 with sigma of 0.02
 F11A-C35 \\sim F10B-C35
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C35, F10A, F11A, F12A, F10B, F11B, F12B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C34, F7A, F8A, F9A, F7B, F8B, F9B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C27, F4A, F5A, F6A, F4B, F5B, F6B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C26, F1A, F2A, F3A, F1B, F2B, F3B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4, C3, C2, C1, C6, C5
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Others
 Sof(F7B)=Sof(F8B)=Sof(F9B)=1-FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=FVAR(1)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(2)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=1-FVAR(3)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(3)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=1-FVAR(4)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(4)
 Fixed Sof: C4(0.5) H4(0.5) C3(0.5) H3(0.5) C2(0.5) H2(0.5) C1(0.5) H1(0.5)
 C6(0.5) H6A(0.5) H6B(0.5) C5(0.5) H5A(0.5) H5B(0.5)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C14(H14), C4(H4), C3(H3), C2(H2), C1(H1)
5.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C12(H12A,H12B), C11(H11A,H11B), C10(H10A,H10B), C9(H9A,H9B),
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
  C7(H7A,H7B), C6(H6A,H6B), C5(H5A,H5B)
5.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C23(H23), C25(H25), C29(H29), C31(H31), C33(H33)
;
_shelx_res_checksum              50868
_shelx_hkl_checksum              56665
_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 1.365
_oxdiff_exptl_absorpt_empirical_full_min 0.603