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_4133303
_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         'C37 H66 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C69 H78 B F24 P2 Rh'
_chemical_formula_weight         1538.97
_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   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                 94.6540(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.30890(10)
_cell_length_b                   17.4465(2)
_cell_length_c                   27.6835(2)
_cell_measurement_reflns_used    37040
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.2700
_cell_measurement_theta_min      3.9490
_cell_volume                     6888.13(11)
_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 0.995
_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  31.00   1.00    3.00    --  -41.77  37.00 -60.00   59
  2  \w    -63.00  28.00   1.00    3.00    --  -41.77  57.00-150.00   91
  3  \w    -62.00 -15.00   1.00    3.00    --  -41.77 -57.00  60.00   47
  4  \w     58.00  97.00   1.00    3.00    --   41.77-125.00-120.00   39
  5  \w   -112.00 -85.00   1.00    3.00    --  -41.77 -57.00  60.00   27
  6  \w     83.00 119.00   1.00   14.00    --  111.00-125.00 -90.00   36
  7  \w     73.00 120.00   1.00   14.00    --  111.00-125.00-120.00   47
  8  \w     63.00 112.00   1.00   14.00    --  111.00-125.00-180.00   49
  9  \w     65.00 106.00   1.00   14.00    --  111.00 -94.00-120.00   41
 10  \w     58.00  90.00   1.00   14.00    --  111.00 -30.00-180.00   32
 11  \w     49.00  75.00   1.00   14.00    --  111.00 -30.00-150.00   26
 12  \w     36.00  85.00   1.00   14.00    --  111.00 -30.00 -60.00   49
 13  \w     39.00  90.00   1.00   14.00    --  111.00 -30.00  30.00   51
 14  \w     70.00 166.00   1.00   14.00    --  111.00  15.00  90.00   96
 15  \w    118.00 168.00   1.00   14.00    --  111.00 125.00  30.00   50
 16  \w     99.00 166.00   1.00   14.00    --  111.00 125.00  60.00   67
 17  \w    109.00 175.00   1.00   14.00    --  111.00 125.00-180.00   66
 18  \w     50.00  89.00   1.00   14.00    --  111.00 -94.00  90.00   39
 19  \w     71.00  96.00   1.00   14.00    --  111.00 -94.00 150.00   25
 20  \w     56.00  99.00   1.00   14.00    --  111.00 -45.00 150.00   43
 21  \w     42.00  68.00   1.00   14.00    --  111.00-125.00-120.00   26
 22  \w   -116.00 -41.00   1.00    3.00    --  -41.77 -19.00 120.00   75
 23  \w    -26.00  18.00   1.00    3.00    --  -41.77  37.00  90.00   44
 24  \w     46.00  72.00   1.00    3.00    --   41.77-125.00 -30.00   26
 25  \w      1.00  63.00   1.00    3.00    --   41.77 -99.00  30.00   62
 26  \w     92.00 121.00   1.00   14.00    --  111.00-125.00  60.00   29
 27  \w     71.00 115.00   1.00   14.00    --  111.00-125.00   0.00   44
 28  \w     42.00  86.00   1.00   14.00    --  111.00 -45.00 -90.00   44
 29  \w     40.00  66.00   1.00   14.00    --  111.00-125.00 -60.00   26
 30  \w     55.00 107.00   1.00   14.00    --  111.00 -94.00  30.00   52
 31  \w     53.00 148.00   1.00   14.00    --  111.00 -15.00  90.00   95
 32  \w    105.00 165.00   1.00   14.00    --  111.00  45.00 -60.00   60
 33  \w     66.00 118.00   1.00   14.00    --  111.00-125.00 150.00   52
 34  \w    112.00 138.00   1.00   14.00    --  111.00 125.00 120.00   26
 35  \w    143.00 174.00   1.00   14.00    --  111.00 125.00 120.00   31
 36  \w    133.00 166.00   1.00   14.00    --  111.00 125.00 -60.00   33
 37  \w     59.00  91.00   1.00   14.00    --  111.00 -30.00 150.00   32
 38  \w     70.00  99.00   1.00   14.00    --  111.00 -45.00 -30.00   29
 39  \w     57.00 106.00   1.00   14.00    --  111.00 -94.00 -60.00   49
 40  \w     41.00  67.00   1.00   14.00    --  111.00 -45.00  90.00   26
 41  \w    109.00 143.00   1.00   14.00    --  111.00  45.00 -30.00   34
 42  \w     95.00 121.00   1.00   14.00    --  111.00-125.00 -60.00   26
 43  \w     59.00  85.00   1.00   14.00    --  111.00 -15.00 -60.00   26
 44  \w    120.00 146.00   1.00   14.00    --  111.00 -15.00 -60.00   26
 45  \w     57.00  83.00   1.00   14.00    --  111.00 -61.00  60.00   26
 46  \w    108.00 134.00   1.00   14.00    --  111.00 -61.00  60.00   26
 47  \w     51.00  80.00   1.00   14.00    --  111.00-125.00  90.00   29
 48  \w     96.00 121.00   1.00   14.00    --  111.00-125.00  90.00   25
 49  \w     36.00  90.00   1.00   14.00    --  111.00 -30.00  90.00   54
;
_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      -0.0390955000
_diffrn_orient_matrix_UB_12      0.0812912000
_diffrn_orient_matrix_UB_13      -0.0098947000
_diffrn_orient_matrix_UB_21      0.0790190000
_diffrn_orient_matrix_UB_22      0.0334723000
_diffrn_orient_matrix_UB_23      0.0348883000
_diffrn_orient_matrix_UB_31      0.0624158000
_diffrn_orient_matrix_UB_32      0.0085446000
_diffrn_orient_matrix_UB_33      -0.0424387000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            90781
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.345
_diffrn_reflns_theta_min         4.004
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.386
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.657
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.484
_exptl_crystal_description       prism
_exptl_crystal_F_000             3152
_exptl_crystal_size_max          0.211
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.077
_refine_diff_density_max         1.431
_refine_diff_density_min         -0.669
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1072
_refine_ls_number_reflns         14355
_refine_ls_number_restraints     732
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0368
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0586P)^2^+5.1179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0984
_refine_ls_wR_factor_ref         0.1018
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13059
_reflns_number_total             14355
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09364_si_002.cif
_cod_data_source_block           4-COD
_cod_database_code               4133303
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C54 H66 Rh1 B1 F24 P2'
_reflns_odcompleteness_completeness 99.95
_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
 F4-F5 \\sim F5-F6 \\sim F6-F4 \\sim F4A-F5A \\sim F5A-F6A \\sim F6A-F4A
 with sigma of 0.4
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22A-F23A \\sim F23A-F24A \\sim
F24A-F22A
 with sigma of 0.4
 F13-F14 \\sim F14-F15 \\sim F15-F13 \\sim F13A-F14A \\sim F14A-F15A \\sim
F15A-F13A
 with sigma of 0.4
 C60-F13 \\sim C60-F14 \\sim C60-F15 \\sim C60-F13A \\sim C60-F14A \\sim
C60-F15A
 with sigma of 0.02
 C69-F22 \\sim C69-F23 \\sim C69-F24 \\sim C69-F22A \\sim C69-F23A \\sim
C69-F24A
 with sigma of 0.02
 C45-F4 \\sim C45-F5 \\sim C45-F6 \\sim C45-F4A \\sim C45-F5A \\sim C45-F6A
 with sigma of 0.02
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1A-F2A \\sim F2A-F3A \\sim F3A-F1A \\sim
F1B-F2B \\sim F2B-F3B \\sim F3B-
 F1B
 with sigma of 0.06
 C44-F1 \\sim C44-F2 \\sim C44-F3 \\sim C44-F1A \\sim C44-F2A \\sim C44-F3A
\\sim F1B-C44 \\sim F2B-C44
 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 0.06
 C52-F10 \\sim C52-F11 \\sim C52-F12 \\sim C52-F10A \\sim C52-F11A \\sim
C52-F12A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C60 \\sim F13 \\sim F14 \\sim F15 \\sim F13A \\sim F14A \\sim F15A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C69 \\sim F22 \\sim F23 \\sim F24 \\sim F22A \\sim F23A \\sim F24A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C45 \\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
C44 \\sim F1 \\sim F2 \\sim F3 \\sim F1B \\sim F2B \\sim F3B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C52 \\sim F10 \\sim F11 \\sim F12 \\sim F10B \\sim F10A \\sim F12B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C60, F13, F14, F15, F13A, F14A, F15A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C69, F22, F23, F24, F22A, F23A, F24A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, F4, F5, F6, F4A, F5A, F6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C44, F1, F2, F3, F1B, F2B, F3B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C52, F10, F11, F12, F10B, F10A, 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 0.00001
 1*[Sof(F1)+Sof(F2)+Sof(F3)]+1*[Sof(F1A)+Sof(F2A)+Sof(F3A)]+1*[Sof(F1B)+
 Sof(F2B)+Sof(F3B)]=1 with esd of 0.00001
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(2)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=FVAR(3)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(4)
 Sof(F4)=Sof(F5)=Sof(F6)=FVAR(4)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(5)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=FVAR(6)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=FVAR(7)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=1-FVAR(8)
 Sof(F13)=Sof(F14)=Sof(F15)=FVAR(8)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(9)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(9)
6.a Ternary CH refined with riding coordinates:
 C6(H6), C5(H5), C2(H2), C1(H1), C14(H14), C20(H20), C26(H26), C32(H32)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C3(H3A,H3B), C8(H8A,H8B), C7(H7A,H7B), C9(H9A,H9B), C10(H10A,
 H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C15(H15A,H15B),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B),
  C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C27(H27A,
 H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B),
 C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B)
6.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C41(H41), C43(H43), C47(H47), C49(H49), C51(H51), C55(H55),
 C57(H57), C59(H59), C63(H63), C65(H65), C67(H67)
;
_shelx_res_checksum              724
_shelx_hkl_checksum              35518
_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 1.423
_oxdiff_exptl_absorpt_empirical_full_min 0.741