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_4133302
_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         'C30 H56 Cl2 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C62 H68 B Cl2 F24 P2 Rh'
_chemical_formula_weight         1515.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_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                 93.3820(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.71870(10)
_cell_length_b                   16.71650(10)
_cell_length_c                   29.1630(2)
_cell_measurement_reflns_used    29059
_cell_measurement_temperature    150.0(4)
_cell_measurement_theta_max      76.0340
_cell_measurement_theta_min      2.6140
_cell_volume                     6676.26(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (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(4)
_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 0.991
_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    -50.00  30.00   1.00    2.00    --  -42.66  38.00   0.00   80
  2  \w     58.00 107.00   1.00    2.00    --   42.66 178.00 -90.00   49
  3  \w   -120.00 -15.00   1.00    2.00    --  -42.66 -19.00-180.00  105
  4  \w    149.00 175.00   1.00    8.00    --  111.00  61.00  60.00   26
  5  \w    144.00 170.00   1.00    8.00    --  111.00  77.00   0.00   26
  6  \w     94.00 128.00   1.00    8.00    --  111.00  61.00  60.00   34
  7  \w     88.00 178.00   1.00    8.00    --  111.00  45.00  30.00   90
  8  \w     87.00 177.00   1.00    8.00    --  111.00  45.00 120.00   90
  9  \w     62.00  92.00   1.00    8.00    --  111.00 -45.00 150.00   30
 10  \w     39.00  64.00   1.00    8.00    --  111.00 -30.00  90.00   25
 11  \w     47.00 138.00   1.00    8.00    --  111.00 -61.00   0.00   91
 12  \w     66.00 136.00   1.00    8.00    --  111.00 -61.00-120.00   70
 13  \w     77.00 103.00   1.00    8.00    --  111.00 -95.00-180.00   26
 14  \w     79.00 109.00   1.00    8.00    --  111.00 -95.00-150.00   30
 15  \w     46.00  88.00   1.00    8.00    --  111.00 -45.00-150.00   42
 16  \w     44.00  79.00   1.00    8.00    --  111.00 -45.00 -90.00   35
 17  \w     36.00  82.00   1.00    8.00    --  111.00 -30.00 -90.00   46
 18  \w     30.00  56.00   1.00    8.00    --  111.00 -95.00-180.00   26
 19  \w     58.00 105.00   1.00    8.00    --  111.00-125.00 120.00   47
 20  \w    -67.00 -41.00   1.00    2.00    --  -42.66  57.00  90.00   26
 21  \w      2.00  27.00   1.00    2.00    --  -42.66  57.00  90.00   25
 22  \w     58.00 128.00   1.00    2.00    --   42.66 178.00-180.00   70
 23  \w     24.00 111.00   1.00    2.00    --   42.66  57.00 -60.00   87
 24  \w    100.00 129.00   1.00    2.00    --   42.66 178.00  30.00   29
 25  \w     95.00 120.00   1.00    8.00    --  111.00 125.00-120.00   25
 26  \w     50.00  90.00   1.00    8.00    --  111.00 -30.00 120.00   40
 27  \w     64.00  99.00   1.00    8.00    --  111.00-125.00-150.00   35
 28  \w     75.00 104.00   1.00    8.00    --  111.00-125.00  60.00   29
 29  \w     88.00 121.00   1.00    8.00    --  111.00-125.00 150.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0294556000
_diffrn_orient_matrix_UB_12      0.0498209000
_diffrn_orient_matrix_UB_13      -0.0414240000
_diffrn_orient_matrix_UB_21      0.0914851000
_diffrn_orient_matrix_UB_22      -0.0525085000
_diffrn_orient_matrix_UB_23      -0.0037330000
_diffrn_orient_matrix_UB_31      -0.0584700000
_diffrn_orient_matrix_UB_32      -0.0570444000
_diffrn_orient_matrix_UB_33      -0.0327119000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0256
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            55334
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.217
_diffrn_reflns_theta_min         3.036
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.203
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74027
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (Rigaku Oxford Diffraction, 2015)
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    1.508
_exptl_crystal_description       block
_exptl_crystal_F_000             3080
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.639
_refine_diff_density_min         -0.490
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     977
_refine_ls_number_reflns         13846
_refine_ls_number_restraints     640
_refine_ls_restrained_S_all      1.138
_refine_ls_R_factor_all          0.0400
_refine_ls_R_factor_gt           0.0372
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0638P)^2^+3.4777P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0991
_refine_ls_wR_factor_ref         0.1020
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12803
_reflns_number_total             13846
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09364_si_002.cif
_cod_data_source_block           4-CH2CL2
_cod_database_code               4133302
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C54 H66 Rh1 P2 B1 F24'
_shelx_estimated_absorpt_t_max   0.518
_shelx_estimated_absorpt_t_min   0.386
_reflns_odcompleteness_completeness 99.94
_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, All F(H) groups
2. Restrained distances
 F4A-C38 \\sim F4B-C38 \\sim F5-C38 \\sim F5B-C38 \\sim F5A-C38 \\sim F6-C38
\\sim F4-C38 \\sim F6B-C38 ~
 F6A-C38
 with sigma of 0.02
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim F6A-F4A \\sim
F4B-F5B \\sim F5B-F6B \\sim F6B-
 F4B
 with sigma of 0.04
 C54-F18A \\sim C54-F16 \\sim C54-F17 \\sim C54-F17A \\sim C54-F16A \\sim
C54-F18
 with sigma of 0.02
 F16-F17 \\sim F17-F18 \\sim F18-F16 \\sim F16A-F17A \\sim F17A-F18A \\sim
F18A-F16A
 with sigma of 0.04
 C37-F2A \\sim C37-F3 \\sim C37-F1A \\sim C37-F1 \\sim C37-F3A \\sim C37-F2
 with sigma of 0.02
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1A-F2A \\sim F2A-F3A \\sim F3A-F1A
 with sigma of 0.04
 C45-F7A \\sim C45-F9 \\sim C45-F8A \\sim C45-F7 \\sim C45-F8 \\sim C45-F9A
 with sigma of 0.02
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F8A-F7A \\sim F7A-F9A \\sim F9A-F8A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
F4 \\sim F5 \\sim F6 \\sim F4A \\sim F5A \\sim F6A \\sim F4B \\sim F6B \\sim
F5B: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01
C54 \\sim F16 \\sim F17 \\sim F18 \\sim F16A \\sim F17A \\sim F18A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C37 \\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
C45 \\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
4. Rigid body (RIGU) restrains
 C38, F4, F5, F6, F4A, F5A, F5A, F6A, F4B, F6B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C54, F16, F17, F18, F16A, F17A, F18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37, F1, F2, F3, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, F7, F8, F9, F7A, F8A, F9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(F4)+Sof(F5)+Sof(F6)]+1*[Sof(F4B)+Sof(F5B)+Sof(F6B)]+1*[Sof(F4A)+
 Sof(F5A)+Sof(F6A)]=1 with esd of 0.0001
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=FVAR(2)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(3)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(4)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(4)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=1-FVAR(5)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(5)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(6)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C6(H6), C12(H12), C18(H18), C24(H24)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C5(H5A,H5B), C7(H7A,H7B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B), C14(H14A,H14B),
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C19(H19A,H19B), C20(H20A,H20B),
  C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C25(H25A,H25B), C26(H26A,
 H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B)
6.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C34(H34), C36(H36), C40(H40), C42(H42), C44(H44), C48(H48),
 C50(H50), C52(H52), C56(H56), C58(H58), C60(H60)
;
_shelx_res_checksum              40804
_shelx_hkl_checksum              9257
_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 1.417
_oxdiff_exptl_absorpt_empirical_full_min 0.785