Modulation of σ-Alkane Interactions in [Rh(L<sub>2</sub>)(alkane)]<sup>+</sup> Solid-State Molecular Organometallic (SMOM) Systems by Variation of the Chelating Phosphine and Alkane: Access to η<sup>2</sup>,η<sup>2</sup>-σ-Alkane Rh(I), η<sup>1</sup>-σ-Alkane Rh(III) Complexes, and Alkane Encapsulation.
Martínez-Martínez, Antonio J; Tegner, Bengt E.; McKay, Alasdair I.; Bukvic, Alexander J.; Rees, Nicholas H.; Tizzard, Graham J.; Coles, Simon J.; Warren, Mark R.; Macgregor, Stuart A.; Weller, Andrew S.; Journal of the American Chemical Society 140 (2018) 14958–14970; doi:10.1021/jacs.8b09364

data_4133297
_publ_section_title
;
 Modulation of \s-Alkane Interactions in
 [Rh(L<sub>2</sub>)(alkane)]<sup>+</sup> Solid-State Molecular
 Organometallic (SMOM) Systems by Variation of the Chelating Phosphine and
 Alkane: Access to \h<sup>2</sup>,\h<sup>2</sup>-\s-Alkane Rh(I),
 \h<sup>1</sup>-\s-Alkane Rh(III) Complexes, and Alkane Encapsulation.
;
_journal_issue                   44
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14958
_journal_page_last               14970
_journal_paper_doi               10.1021/jacs.8b09364
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C35 H60 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C67 H72 B F24 P2 Rh'
_chemical_formula_weight         1508.90
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.1100(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.47695(14)
_cell_length_b                   17.24051(12)
_cell_length_c                   20.25038(14)
_cell_measurement_reflns_used    22399
_cell_measurement_temperature    149.9(3)
_cell_measurement_theta_max      76.2140
_cell_measurement_theta_min      3.3810
_cell_volume                     6782.44(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (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      149.9(3)
_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 0.996
_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     98.00 129.00   1.00    1.50    --   42.66 178.00 -60.00   31
  2  \w    -43.00  25.00   1.00    1.50    --  -42.66  38.00 -30.00   68
  3  \w    -49.00  11.00   1.00    1.50    --  -42.66  38.00 120.00   60
  4  \w   -116.00 -12.00   1.00    1.50    --  -42.66 -77.00  30.00  104
  5  \w    134.00 170.00   1.00    6.00    --  111.00  77.00 -30.00   36
  6  \w    137.00 177.00   1.00    6.00    --  111.00  15.00  60.00   40
  7  \w    113.00 138.00   1.00    6.00    --  111.00 -61.00 -90.00   25
  8  \w     84.00 134.00   1.00    6.00    --  111.00 -77.00 -90.00   50
  9  \w     95.00 121.00   1.00    6.00    --  111.00-125.00  30.00   26
 10  \w     61.00  86.00   1.00    6.00    --  111.00 -61.00 -90.00   25
 11  \w     54.00  80.00   1.00    6.00    --  111.00 -95.00 -90.00   26
 12  \w     49.00 114.00   1.00    6.00    --  111.00-125.00 -30.00   65
 13  \w     68.00 120.00   1.00    6.00    --  111.00-125.00-150.00   52
 14  \w     40.00  66.00   1.00    6.00    --  111.00 -30.00   0.00   26
 15  \w     66.00 116.00   1.00    6.00    --  111.00  15.00  60.00   50
 16  \w    100.00 159.00   1.00    6.00    --  111.00  45.00  30.00   59
 17  \w     91.00 177.00   1.00    6.00    --  111.00  30.00 -60.00   86
 18  \w     80.00 114.00   1.00    6.00    --  111.00  77.00 -30.00   34
 19  \w     56.00  98.00   1.00    6.00    --  111.00 -45.00 150.00   42
 20  \w     41.00  74.00   1.00    6.00    --  111.00-125.00 120.00   33
 21  \w     36.00 109.00   1.00    6.00    --  111.00 -95.00  60.00   73
 22  \w    -48.00  30.00   1.00    1.50    --  -42.66  38.00-180.00   78
 23  \w    -43.00  13.00   1.00    1.50    --  -42.66  38.00 -90.00   56
 24  \w     98.00 127.00   1.00    1.50    --   42.66-178.00 120.00   29
 25  \w     73.00  99.00   1.00    1.50    --   42.66 178.00-180.00   26
 26  \w     82.00 108.00   1.00    1.50    --   42.66 178.00 -60.00   26
 27  \w     42.00  79.00   1.00    6.00    --  111.00 -95.00-150.00   37
 28  \w     90.00 121.00   1.00    6.00    --  111.00-125.00 -60.00   31
 29  \w    111.00 137.00   1.00    6.00    --  111.00 125.00-120.00   26
 30  \w    143.00 176.00   1.00    6.00    --  111.00  77.00 -60.00   33
 31  \w    111.00 139.00   1.00    6.00    --  111.00 -61.00-120.00   28
 32  \w     95.00 121.00   1.00    6.00    --  111.00-125.00  60.00   26
 33  \w     78.00 104.00   1.00    6.00    --  111.00-125.00-180.00   26
 34  \w     72.00  98.00   1.00    6.00    --  111.00 -95.00  30.00   26
 35  \w     83.00 108.00   1.00    6.00    --  111.00  77.00-120.00   25
 36  \w    121.00 173.00   1.00    6.00    --  111.00 125.00-150.00   52
 37  \w     55.00  84.00   1.00    6.00    --  111.00 -61.00-120.00   29
 38  \w     77.00 106.00   1.00    6.00    --  111.00-125.00 -90.00   29
 39  \w    147.00 174.00   1.00    6.00    --  111.00  77.00   0.00   27
 40  \w    129.00 157.00   1.00    6.00    --  111.00  77.00-120.00   28
 41  \w     72.00 107.00   1.00    6.00    --  111.00 -95.00-180.00   35
 42  \w     31.00  82.00   1.00    6.00    --  111.00 -15.00 150.00   51
 43  \w     41.00 121.00   1.00    6.00    --  111.00-125.00 150.00   80
 44  \w     99.00 125.00   1.00    6.00    --  111.00  77.00   0.00   26
 45  \w     36.00  91.00   1.00    6.00    --  111.00 -30.00  90.00   55
 46  \w     63.00  89.00   1.00    6.00    --  111.00 -30.00 -30.00   26
 47  \w     63.00  99.00   1.00    6.00    --  111.00 -45.00  60.00   36
 48  \w     72.00  98.00   1.00    6.00    --  111.00 -95.00 -60.00   26
 49  \w     87.00 144.00   1.00    6.00    --  111.00  45.00 -30.00   57
 50  \w     31.00  57.00   1.00    6.00    --  111.00 -95.00 -90.00   26
;
_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      -0.0021957000
_diffrn_orient_matrix_UB_12      0.0863195000
_diffrn_orient_matrix_UB_13      0.0194589000
_diffrn_orient_matrix_UB_21      -0.0419046000
_diffrn_orient_matrix_UB_22      -0.0207853000
_diffrn_orient_matrix_UB_23      0.0592389000
_diffrn_orient_matrix_UB_31      0.0672652000
_diffrn_orient_matrix_UB_32      -0.0100168000
_diffrn_orient_matrix_UB_33      0.0439687000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            42555
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.231
_diffrn_reflns_theta_min         3.427
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.428
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58141
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.478
_exptl_crystal_description       prism
_exptl_crystal_F_000             3080
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.763
_refine_diff_density_min         -0.582
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     646
_refine_ls_number_reflns         7090
_refine_ls_number_restraints     950
_refine_ls_restrained_S_all      1.343
_refine_ls_R_factor_all          0.0538
_refine_ls_R_factor_gt           0.0513
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0737P)^2^+17.5446P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1354
_refine_ls_wR_factor_ref         0.1382
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6651
_reflns_number_total             7090
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09364_si_002.cif
_cod_data_source_block           3-NBD
_cod_original_cell_volume        6782.43(8)
_cod_database_code               4133297
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'Rh C62 H56 B F24'
_shelx_estimated_absorpt_t_max   0.795
_shelx_estimated_absorpt_t_min   0.436
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C14-C19 \\sim C14-C15 \\sim C15-C16 \\sim C16-C17 \\sim C17-C18 \\sim C18-C19
 with sigma of 0.02
 C14A-C19A \\sim C14A-C15A \\sim C16A-C15A \\sim C18A-C19A \\sim C16A-C17A
\\sim C17A-C18A
 with sigma of 0.02
 F9-F8 \\sim F9-F7 \\sim F8-F7 \\sim F8A-F9A \\sim F8A-F7A \\sim F9A-F7A
 with sigma of 0.04
 F3A-F1A \\sim F3A-F2A \\sim F3-F1 \\sim F3-F2 \\sim F1-F2 \\sim F1A-F2A
 with sigma of 0.04
 C30-F3A \\sim C30-F3 \\sim C30-F1 \\sim C30-F1A \\sim C30-F2A \\sim C30-F2
 with sigma of 0.02
 C38-F9 \\sim C38-F8 \\sim C38-F7 \\sim C38-F8A \\sim C38-F9A \\sim C38-F7A
 with sigma of 0.02
 F12A-F11A \\sim F12A-F10A \\sim F12-F11 \\sim F12-F10 \\sim F11A-F10A \\sim
F11-F10
 with sigma of 0.04
 C39-F12A \\sim C39-F12 \\sim C39-F11A \\sim C39-F11 \\sim C39-F10A \\sim
C39-F10
 with sigma of 0.02
 P1-C14 \\sim P1-C14A
 with sigma of 0.02
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim F6A-F4A
 with sigma of 0.04
 C31-F4A \\sim C31-F4 \\sim C31-F6A \\sim C31-F6 \\sim C31-F5 \\sim C31-F5A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C14 \\sim C19 \\sim C18 \\sim C17 \\sim C16 \\sim C15 \\sim C16A \\sim C14A
\\sim C19A \\sim C18A \\sim C17A \\sim C15A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C30 \\sim F1 \\sim F2 \\sim F3 \\sim F1A \\sim F2A \\sim F3A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C38 \\sim F7 \\sim F8 \\sim F9 \\sim F7A \\sim F8A \\sim F9A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C39 \\sim F10 \\sim F11 \\sim F12 \\sim F10A \\sim F11A \\sim F12A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C31 \\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
C7 \\sim C1 \\sim C2 \\sim C3 \\sim C6 \\sim C4 \\sim C5 \\sim C7 \\sim C1
\\sim C2 \\sim C3 \\sim C6 \\sim C4 \\sim C5: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C14, C19, C18, C17, C16, C15, C16A, C14A, C19A, C18A, C17A, C15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C30, F1, F2, F3, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C38, F7, F8, F9, F7A, F8A, F9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C39, F10, F11, F12, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, F4, F5, F6, F4A, F5A, F6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C1, C2, C3, C6, C4, C5, C7, C1, C2, C3, C6, C4, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C16A)=Sof(H16C)=Sof(H16D)=Sof(C14A)=Sof(H14A)=Sof(C19A)=Sof(H19C)=
 Sof(H19D)=Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(C17A)=Sof(H17C)=Sof(H17D)=
 Sof(C15A)=Sof(H15C)=Sof(H15D)=1-FVAR(1)
 Sof(C14)=Sof(H14)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C15)=Sof(H15A)=
 Sof(H15B)=FVAR(1)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(2)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(4)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(4)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(5)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(5)
 Fixed Sof: C20(0.5) H20A(0.5) H20B(0.5) C23(0.5) H23A(0.5) H23B(0.5) C21(0.5)
 H21A(0.5) H21B(0.5) C22(0.5) H22A(0.5) H22B(0.5) C7(0.5) H7A(0.5) H7B(0.5)
 C1(0.5) H1(0.5) C2(0.5) H2(0.5) C3(0.5) H3(0.5) C6(0.5) H6(0.5) C4(0.5)
 H4(0.5) C5(0.5) H5(0.5)
6.a Ternary CH refined with riding coordinates:
 C8(H8), C14(H14), C14A(H14A), C1(H1), C2(H2), C3(H3), C6(H6), C4(H4), C5(H5)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C12(H12A,H12B), C11(H11A,H11B), C10(H10A,H10B), C9(H9A,H9B),
 C19(H19A,H19B), C18(H18A,H18B), C17(H17A,H17B), C16(H16A,H16B), C15(H15A,H15B),
  C16A(H16C,H16D), C19A(H19C,H19D), C18A(H18C,H18D), C17A(H17C,H17D), C15A(H15C,
 H15D), C20(H20A,H20B), C23(H23A,H23B), C21(H21A,H21B), C22(H22A,H22B), C7(H7A,
 H7B)
6.c Aromatic/amide H refined with riding coordinates:
 C25(H25), C27(H27), C29(H29), C37(H37), C35(H35), C33(H33)
;
_shelx_res_checksum              23795
_shelx_hkl_checksum              79539
_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 1.596
_oxdiff_exptl_absorpt_empirical_full_min 0.764