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_4133295
_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 H62 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C67 H74 B F24 P2 Rh'
_chemical_formula_weight         1510.92
_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                 92.8450(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.4403(2)
_cell_length_b                   17.1515(2)
_cell_length_c                   20.2397(2)
_cell_measurement_reflns_used    21769
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.3390
_cell_measurement_theta_min      4.0930
_cell_volume                     6740.21(12)
_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      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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    131.00 163.00   1.00    8.00    --  111.00  77.00   0.00   32
  2  \w    117.00 163.00   1.00    8.00    --  111.00  45.00 -60.00   46
  3  \w    108.00 170.00   1.00    8.00    --  111.00 111.00  30.00   62
  4  \w    100.00 156.00   1.00    8.00    --  111.00 111.00 -30.00   56
  5  \w     86.00 176.00   1.00    8.00    --  111.00  15.00 -90.00   90
  6  \w    107.00 134.00   1.00    8.00    --  111.00 -61.00   0.00   27
  7  \w     97.00 142.00   1.00    8.00    --  111.00 -77.00 -30.00   45
  8  \w     97.00 141.00   1.00    8.00    --  111.00 -77.00 -90.00   44
  9  \w     94.00 136.00   1.00    8.00    --  111.00 -77.00-150.00   42
 10  \w     83.00 109.00   1.00    8.00    --  111.00 -94.00 -60.00   26
 11  \w     91.00 116.00   1.00    8.00    --  111.00-111.00 -30.00   25
 12  \w     88.00 114.00   1.00    8.00    --  111.00-111.00  30.00   26
 13  \w     80.00 114.00   1.00    8.00    --  111.00-111.00 120.00   34
 14  \w     70.00  99.00   1.00    8.00    --  111.00-111.00 150.00   29
 15  \w     58.00 109.00   1.00    8.00    --  111.00-111.00  90.00   51
 16  \w     56.00  82.00   1.00    8.00    --  111.00 -61.00   0.00   26
 17  \w     60.00  88.00   1.00    8.00    --  111.00 -45.00 -60.00   28
 18  \w     45.00  77.00   1.00    8.00    --  111.00 -77.00-150.00   32
 19  \w     55.00 104.00   1.00    8.00    --  111.00 -94.00-180.00   49
 20  \w     56.00 116.00   1.00    8.00    --  111.00-111.00-180.00   60
 21  \w     56.00  81.00   1.00    2.00    --   41.77 -99.00-180.00   25
 22  \w     18.00  45.00   1.00    2.00    --   41.77 -99.00-180.00   27
 23  \w     43.00 116.00   1.00    8.00    --  111.00-111.00 -90.00   73
 24  \w     47.00  72.00   1.00    8.00    --  111.00 -30.00-180.00   25
 25  \w     36.00  90.00   1.00    8.00    --  111.00 -30.00 -90.00   54
 26  \w     40.00  77.00   1.00    8.00    --  111.00 -77.00 -30.00   37
 27  \w     37.00  74.00   1.00    8.00    --  111.00-111.00 -30.00   37
 28  \w     44.00  89.00   1.00    8.00    --  111.00 -45.00  60.00   45
 29  \w     36.00  64.00   1.00    8.00    --  111.00 -30.00  60.00   28
 30  \w     38.00  84.00   1.00    8.00    --  111.00 -30.00  90.00   46
 31  \w     38.00  91.00   1.00    8.00    --  111.00 -30.00   0.00   53
 32  \w     30.00  62.00   1.00    8.00    --  111.00 -94.00 -60.00   32
 33  \w     24.00  97.00   1.00    2.00    --   41.77-125.00 150.00   73
 34  \w     90.00 147.00   1.00    8.00    --  111.00  30.00 150.00   57
 35  \w     82.00 176.00   1.00    8.00    --  111.00  77.00 150.00   94
 36  \w     80.00 111.00   1.00    8.00    --  111.00  77.00   0.00   31
 37  \w    -30.00  20.00   1.00    2.00    --  -41.77  37.00-120.00   50
 38  \w    -32.00  -6.00   1.00    2.00    --  -41.77  37.00 -60.00   26
 39  \w    -73.00  31.00   1.00    2.00    --  -41.77  77.00 -30.00  104
 40  \w    -48.00  26.00   1.00    2.00    --  -41.77  37.00  90.00   74
 41  \w    -45.00 -20.00   1.00    2.00    --  -41.77 -37.00 120.00   25
 42  \w    -83.00  29.00   1.00    2.00    --  -41.77   0.00-150.00  112
;
_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      0.0015949000
_diffrn_orient_matrix_UB_12      0.0891595000
_diffrn_orient_matrix_UB_13      -0.0092134000
_diffrn_orient_matrix_UB_21      0.0434997000
_diffrn_orient_matrix_UB_22      0.0082843000
_diffrn_orient_matrix_UB_23      0.0653679000
_diffrn_orient_matrix_UB_31      0.0663274000
_diffrn_orient_matrix_UB_32      -0.0075164000
_diffrn_orient_matrix_UB_33      -0.0380393000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0262
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            40800
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.309
_diffrn_reflns_theta_min         4.014
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.449
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68861
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_description       prism
_exptl_crystal_F_000             3088
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.809
_refine_diff_density_min         -0.865
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     670
_refine_ls_number_reflns         7045
_refine_ls_number_restraints     1198
_refine_ls_restrained_S_all      1.259
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0392
_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^)+(0.0511P)^2^+13.5108P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1004
_refine_ls_wR_factor_ref         0.1015
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6786
_reflns_number_total             7045
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09364_si_002.cif
_cod_data_source_block           2-COD
_cod_database_code               4133295
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'Rh C46 H56 B F24 P2'
_shelx_estimated_absorpt_t_max   0.644
_shelx_estimated_absorpt_t_min   0.517
_reflns_odcompleteness_completeness 99.96
_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
 C12A-C11A \\sim C12-C11 \\sim C13-C12 \\sim C13A-C12A \\sim C14A-C13A \\sim
C14-C13 \\sim C15-C14 ~
 C15A-C14A \\sim C16-C15 \\sim C16A-C15A \\sim C16-C11 \\sim C16A-C11A
 with sigma of 0.02
 P1-C11 \\sim P1-C11A \\sim P1-C5
 with sigma of 0.02
 F7-F8 \\sim F7-F9 \\sim F8-F9 \\sim F7A-F9A \\sim F7A-F8A \\sim F9A-F8A
 with sigma of 0.04
 F8-F7 \\sim F8-F9 \\sim F9A-F7A \\sim F7A-F8A
 with sigma of 0.04
 C34-F8 \\sim C34-F9A \\sim C34-F7 \\sim C34-F7A \\sim C34-F9 \\sim C34-F8A
 with sigma of 0.02
 F10A-F12A \\sim F10A-F11A \\sim F10-F12 \\sim F10-F11 \\sim F12A-F11A \\sim
F12-F11
 with sigma of 0.04
 C35-F10A \\sim C35-F10 \\sim C35-F12A \\sim C35-F12 \\sim C35-F11 \\sim
C35-F11A
 with sigma of 0.02
 F1A-F2B \\sim F1A-F3A \\sim F1A-F3B \\sim F1A-F2A \\sim F1B-F3A \\sim F1B-F3B
\\sim F1B-F2A \\sim F3-F1 ~
 F2B-F3B \\sim F2B-F2A \\sim F2-F1 \\sim F3A-F3B \\sim F3A-F2A
 with sigma of 0.04
 C26-F1A \\sim C26-F1B \\sim C26-F3 \\sim C26-F2B \\sim C26-F2 \\sim C26-F3A
\\sim C26-F1 \\sim C26-F3B ~
 C26-F2A
 with sigma of 0.02
 C27-F5A \\sim C27-F4 \\sim C27-F6 \\sim C27-F6A \\sim C27-F5 \\sim C27-F4A
 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 0.02
3. Rigid bond restraints
 C11, C12, C13, C14, C15, C16, C11A, C12A, C13A, C14A, C15A, C16A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C34, F7, F8, F9, F7A, F8A, F9A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
 C26, F1, F2, F3, F1B, F2B, F3B, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C27, F4, F5, F6, F4A, F5A, F6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C17 \\sim C17 \\sim C18 \\sim C18 \\sim C19 \\sim C19: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C11A \\sim C12A
\\sim C13A \\sim C14A \\sim C15A \\sim C16A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.01
C34 \\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
C35 \\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
C26 \\sim F1 \\sim F2 \\sim F3 \\sim F1B \\sim F2B \\sim F3B \\sim F1A \\sim
F2A \\sim F3A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C27 \\sim F4 \\sim F5 \\sim F6 \\sim F4A \\sim F5A \\sim F6A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C1A \\sim C2A \\sim C3A \\sim C4A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C19) = Uanis(C17)
5. Rigid body (RIGU) restrains
 C17, C17, C18, C18, C19, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C12, C13, C14, C15, C16, C11A, C12A, C13A, C14A, C15A, C16A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C34, F7, F8, F9, F7A, F8A, F9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C35, F10, F11, F12, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, F1, F2, F3, F1B, F2B, F3B, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, F4, F5, F6, F4A, F5A, F6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C2, C3, C4, C1A, C2A, C3A, C4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(F1A)+Sof(F2A)+Sof(F3A)]+1*[Sof(F1)+Sof(F2)+Sof(F3)]+1*[Sof(F1B)+
 Sof(F2B)+Sof(F3B)]=1 with esd of 0.0001
 Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C13A)=Sof(H13C)=
 Sof(H13D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=
 Sof(C16A)=Sof(H16C)=Sof(H16D)=1-FVAR(1)
 Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=Sof(H13B)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=
 Sof(H16B)=FVAR(1)
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=
 Sof(H4AA)=Sof(H4AB)=1-FVAR(2)
 Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=
 Sof(H4B)=FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(3)
 Sof(F4)=Sof(F5)=Sof(F6)=1-FVAR(4)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=FVAR(4)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(5)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(5)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(6)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(6)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(7)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=FVAR(8)
 Fixed Sof: C17(0.5) H17A(0.5) H17B(0.5) C18(0.5) H18A(0.5) H18B(0.5) C19(0.5)
 H19A(0.5) H19B(0.5)
7.a Ternary CH refined with riding coordinates:
 C5(H5), C1(H1), C2(H2), C11(H11), C1A(H1A), C2A(H2A), C11A(H11A)
7.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C3(H3A,
 H3B), C4(H4A,H4B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,
 H15B), C16(H16A,H16B), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C12A(H12C,H12D),
 C13A(H13C,H13D), C14A(H14C,H14D), C15A(H15C,H15D), C16A(H16C,H16D), C17(H17A,
 H17B), C18(H18A,H18B), C19(H19A,H19B)
7.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C23(H23), C25(H25), C29(H29), C31(H31), C33(H33)
;
_shelx_res_checksum              72869
_shelx_hkl_checksum              95430
_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 1.363
_oxdiff_exptl_absorpt_empirical_full_min 0.707