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_4133298
_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 H64 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C67 H76 B F24 P2 Rh'
_chemical_formula_weight         1512.93
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                 92.2234(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.00320(12)
_cell_length_b                   18.02691(11)
_cell_length_c                   20.06660(11)
_cell_measurement_reflns_used    39280
_cell_measurement_temperature    150.0(4)
_cell_measurement_theta_max      76.1490
_cell_measurement_theta_min      3.1040
_cell_volume                     6869.02(7)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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 0.999
_diffrn_measured_fraction_theta_max 0.993
_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    -28.00  -1.00   1.00    1.50    --  -42.41  38.00  30.00   27
  2  \w    -42.00   5.00   1.00    1.50    --  -42.41  37.00-128.00   47
  3  \w    -99.00  -9.00   1.00    1.50    --  -42.41 -19.00  60.00   90
  4  \w     97.00 124.00   1.00    1.50    --   42.41 178.00-150.00   27
  5  \w     57.00 129.00   1.00    1.50    --   42.41 178.00  30.00   72
  6  \w    107.00 134.00   1.00    6.00    --  111.00 125.00 120.00   27
  7  \w    150.00 175.00   1.00    6.00    --  111.00 125.00 120.00   25
  8  \w     90.00 176.00   1.00    6.00    --  111.00  45.00 -60.00   86
  9  \w    145.00 176.00   1.00    6.00    --  111.00  30.00-180.00   31
 10  \w    103.00 139.00   1.00    6.00    --  111.00 -61.00-180.00   36
 11  \w     95.00 121.00   1.00    6.00    --  111.00-125.00-120.00   26
 12  \w     77.00 121.00   1.00    6.00    --  111.00-125.00 -60.00   44
 13  \w     74.00  99.00   1.00    6.00    --  111.00 -95.00  30.00   25
 14  \w     81.00 117.00   1.00    6.00    --  111.00-125.00  30.00   36
 15  \w     47.00  91.00   1.00    6.00    --  111.00 -45.00 -90.00   44
 16  \w     64.00  99.00   1.00    6.00    --  111.00 -95.00-150.00   35
 17  \w     52.00  78.00   1.00    6.00    --  111.00 -30.00-180.00   26
 18  \w     43.00  81.00   1.00    6.00    --  111.00 -61.00-180.00   38
 19  \w     41.00  99.00   1.00    6.00    --  111.00 -45.00-180.00   58
 20  \w     39.00 105.00   1.00    6.00    --  111.00-125.00-150.00   66
 21  \w     36.00  61.00   1.00    6.00    --  111.00 -30.00   0.00   25
 22  \w     40.00  81.00   1.00    6.00    --  111.00 -30.00  30.00   41
 23  \w     31.00  56.00   1.00    6.00    --  111.00 -95.00  30.00   25
 24  \w     95.00 178.00   1.00    6.00    --  111.00  45.00-150.00   83
 25  \w    -94.00  -5.00   1.00    1.50    --  -42.41 -19.00 150.00   89
 26  \w      3.00  81.00   1.00    1.50    --   42.41 -99.00  60.00   78
 27  \w     88.00 124.00   1.00    1.50    --   42.41 178.00 -60.00   36
 28  \w    114.00 139.00   1.00    6.00    --  111.00 -61.00  60.00   25
 29  \w    146.00 178.00   1.00    6.00    --  111.00  30.00 150.00   32
 30  \w    111.00 177.00   1.00    6.00    --  111.00  30.00 -90.00   66
 31  \w     96.00 126.00   1.00    6.00    --  111.00  30.00 150.00   30
 32  \w     74.00 120.00   1.00    6.00    --  111.00-125.00-180.00   46
 33  \w     62.00  96.00   1.00    6.00    --  111.00 -45.00 -60.00   34
 34  \w     76.00 120.00   1.00    6.00    --  111.00-125.00   0.00   44
 35  \w    109.00 135.00   1.00    6.00    --  111.00  45.00 -30.00   26
 36  \w    153.00 178.00   1.00    6.00    --  111.00  45.00 -30.00   25
 37  \w     40.00  78.00   1.00    6.00    --  111.00 -45.00  90.00   38
 38  \w     67.00  93.00   1.00    6.00    --  111.00 -45.00   0.00   26
 39  \w     83.00 108.00   1.00    6.00    --  111.00-125.00 -30.00   25
 40  \w     42.00  68.00   1.00    6.00    --  111.00-125.00 -30.00   26
 41  \w     45.00  83.00   1.00    6.00    --  111.00 -77.00  90.00   38
 42  \w     98.00 125.00   1.00    6.00    --  111.00 -77.00  90.00   27
 43  \w     93.00 119.00   1.00    6.00    --  111.00  45.00-120.00   26
 44  \w    139.00 171.00   1.00    6.00    --  111.00  45.00-120.00   32
 45  \w    117.00 142.00   1.00    6.00    --  111.00 -77.00 -90.00   25
 46  \w     95.00 121.00   1.00    6.00    --  111.00-125.00  90.00   26
 47  \w     50.00 109.00   1.00    6.00    --  111.00 -95.00  60.00   59
 48  \w     89.00 116.00   1.00    6.00    --  111.00  45.00-180.00   27
 49  \w    120.00 148.00   1.00    6.00    --  111.00  45.00-180.00   28
 50  \w     44.00  71.00   1.00    6.00    --  111.00 -30.00 -30.00   27
 51  \w     48.00  82.00   1.00    6.00    --  111.00 -95.00  90.00   34
 52  \w    105.00 130.00   1.00    6.00    --  111.00 125.00 -90.00   25
 53  \w     86.00 112.00   1.00    6.00    --  111.00 -61.00  60.00   26
;
_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      -0.0713125000
_diffrn_orient_matrix_UB_12      0.0240991000
_diffrn_orient_matrix_UB_13      -0.0321705000
_diffrn_orient_matrix_UB_21      0.0177294000
_diffrn_orient_matrix_UB_22      0.0816493000
_diffrn_orient_matrix_UB_23      0.0160602000
_diffrn_orient_matrix_UB_31      0.0343716000
_diffrn_orient_matrix_UB_32      0.0078804000
_diffrn_orient_matrix_UB_33      -0.0678678000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            88409
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.264
_diffrn_reflns_theta_min         4.657
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.385
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'reddish violet'
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.463
_exptl_crystal_description       prism
_exptl_crystal_F_000             3096
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.241
_refine_diff_density_min         -0.532
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1128
_refine_ls_number_reflns         14284
_refine_ls_number_restraints     1162
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0388
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0743P)^2^+2.7363P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1024
_refine_ls_wR_factor_ref         0.1067
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13047
_reflns_number_total             14284
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09364_si_002.cif
_cod_data_source_block           3-NBA
_cod_database_code               4133298
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C67 H79 P2 Rh1 F24 B1'
_shelx_estimated_absorpt_t_max   0.728
_shelx_estimated_absorpt_t_min   0.440
_reflns_odcompleteness_completeness 99.97
_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
2. Restrained distances
 C50-F7 \\sim C50-F8 \\sim C50-F9 \\sim C50-F7A \\sim C50-F8A \\sim C50-F9A
 with sigma of 0.02
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.02
 C59-F16 \\sim C59-F17 \\sim C59-F18 \\sim C59-F16A \\sim C59-F17A \\sim
C59-F18A
 with sigma of 0.02
 C59-F16 \\sim C59-F17 \\sim C59-F18 \\sim C59-F16B \\sim C59-F17B \\sim
C59-F18B
 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 0.02
 F16-F17 \\sim F17-F18 \\sim F18-F16 \\sim F16B-F17B \\sim F17B-F18B \\sim
F18B-F16B
 with sigma of 0.02
 C67-F22 \\sim C67-F23 \\sim C67-F24 \\sim C67-F22A \\sim C67-F23A \\sim
C67-F24A
 with sigma of 0.02
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22A-F23A \\sim F23A-F24A \\sim
F24A-F22A
 with sigma of 0.02
 C67-F22 \\sim C67-F23 \\sim C67-F24 \\sim C67-F22B \\sim C67-F23B \\sim
C67-F24B
 with sigma of 0.02
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22B-F23B \\sim F23B-F24B \\sim
F24B-F22B
 with sigma of 0.02
 C66-F19 \\sim C66-F20 \\sim C66-F21 \\sim C66-F19A \\sim C66-F20A \\sim
C66-F21A
 with sigma of 0.02
 C66-F19 \\sim C66-F20 \\sim C66-F21 \\sim C66-F19B \\sim C66-F20B \\sim
C66-F21B
 with sigma of 0.02
 F19-F20 \\sim F20-F21 \\sim F21-F19 \\sim F19A-F20A \\sim F20A-F21A \\sim
F21A-F19A
 with sigma of 0.02
 F19-F20 \\sim F20-F21 \\sim F21-F19 \\sim F19B-F20B \\sim F20B-F21B \\sim
F21B-F19B
 with sigma of 0.02
 C51-F10 \\sim C51-F11 \\sim C51-F12 \\sim C51-F10A \\sim C51-F11A \\sim
C51-F12A
 with sigma of 0.02
 C51-F10 \\sim C51-F11 \\sim C51-F12 \\sim C51-F10B \\sim C51-F11B \\sim
C51-F12B
 with sigma of 0.02
 F10-F11 \\sim F11-F12 \\sim F12-F10 \\sim F10A-F11A \\sim F11A-F12A \\sim
F12A-F10A
 with sigma of 0.02
 F10-F11 \\sim F11-F12 \\sim F12-F10 \\sim F10B-F11B \\sim F11B-F12B \\sim
F12B-F10B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C50 \\sim F7 \\sim F8 \\sim F9 \\sim F7A \\sim F8A \\sim F9A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C59 \\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
C59 \\sim F16 \\sim F17 \\sim F18 \\sim F16B \\sim F17B \\sim F18B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C67 \\sim F22 \\sim F23 \\sim F24 \\sim F22A \\sim F23A \\sim F24A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C67 \\sim F22 \\sim F23 \\sim F24 \\sim F22B \\sim F23B \\sim F24B: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C66 \\sim F19 \\sim F20 \\sim F21 \\sim F19A \\sim F20A \\sim F21A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C66 \\sim F19 \\sim F20 \\sim F21 \\sim F19B \\sim F20B \\sim F21B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C51 \\sim F10 \\sim F11 \\sim F12 \\sim F10A \\sim F11A \\sim F12A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C51 \\sim F10 \\sim F11 \\sim F12 \\sim F10B \\sim F11B \\sim F12B: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(F19A) \\sim Ueq, Uanis(F19B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F19) \\sim Ueq, Uanis(F19A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C50, F7, F8, F9, F7A, F8A, F9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C59, F16, F17, F18, F16A, F17A, F18A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C59, F16, F17, F18, F16B, F17B, F18B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C67, F22, F23, F24, F22A, F23A, F24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C67, F22, F23, F24, F22B, F23B, F24B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C66, F19, F20, F21, F19A, F20A, F21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C66, F19, F20, F21, F19B, F20B, F21B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C51, F10, F11, F12, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C51, F10, F11, F12, F10B, F11B, F12B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(F10)+Sof(F11)+Sof(F12)]+1*[Sof(F10A)+Sof(F11A)+Sof(F12A)]+1*[Sof(F10B)+
 Sof(F11B)+Sof(F12B)]=1 with esd of 0.0001
 1*[Sof(F16)+Sof(F17)+Sof(F18)]+1*[Sof(F16A)+Sof(F17A)+Sof(F18A)]+1*[Sof(F16B)+
 Sof(F17B)+Sof(F18B)]=1 with esd of 0.0001
 1*[Sof(F19)+Sof(F20)+Sof(F21)]+1*[Sof(F19A)+Sof(F20A)+Sof(F21A)]+1*[Sof(F19B)+
 Sof(F20B)+Sof(F21B)]=1 with esd of 0.0001
 1*[Sof(F22)+Sof(F23)+Sof(F24)]+1*[Sof(F22A)+Sof(F23A)+Sof(F24A)]+1*[Sof(F22B)+
 Sof(F23B)+Sof(F24B)]=1 with esd of 0.0001
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(1)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(1)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(2)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(3)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=FVAR(4)
 Sof(F16)=Sof(F17)=Sof(F18)=FVAR(5)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=FVAR(6)
 Sof(F16B)=Sof(F17B)=Sof(F18B)=FVAR(7)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(8)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=FVAR(9)
 Sof(F19B)=Sof(F20B)=Sof(F21B)=FVAR(10)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(11)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=FVAR(12)
 Sof(F22B)=Sof(F23B)=Sof(F24B)=FVAR(13)
6.a Ternary CH refined with riding coordinates:
 C3(H3), C6(H6), C12(H12), C18(H18), C24(H24), C30(H30)
6.b Secondary CH2 refined with riding coordinates:
 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), C31(H31A,H31B), C32(H32A,H32B),
 C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B)
6.c Aromatic/amide H refined with riding coordinates:
 C37(H37), C39(H39), C41(H41), C45(H45), C47(H47), C49(H49), C53(H53),
 C55(H55), C57(H57), C61(H61), C63(H63), C65(H65)
;
_shelx_res_checksum              20627
_shelx_hkl_checksum              28848
_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 1.577
_oxdiff_exptl_absorpt_empirical_full_min 0.670