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_4133293
_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
'0.5(C34 H58 P2 Rh), 0.25(C132 H140 B2 F48 P4 Rh2), 0.5(C32 H12 B F24)'
_chemical_formula_sum            'C66 H70 B F24 P2 Rh'
_chemical_formula_weight         1494.88
_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                 94.0077(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.5269(2)
_cell_length_b                   34.2076(4)
_cell_length_c                   20.0095(2)
_cell_measurement_reflns_used    25557
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.3010
_cell_measurement_theta_min      3.4590
_cell_volume                     13333.0(2)
_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      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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     24.00  51.00   1.00    4.00    --   41.65-125.00  30.00   27
  2  \w     35.00  85.00   1.00    4.00    --   41.65-125.00 -30.00   50
  3  \w   -128.00  32.00   1.00    4.00    --  -41.65   0.00  30.00  160
  4  \w     76.00 138.00   1.00   16.00    --  111.00 -61.00-120.00   62
  5  \w    108.00 133.00   1.00   16.00    --  111.00 -77.00-120.00   25
  6  \w     88.00 132.00   1.00   16.00    --  111.00 -15.00 -30.00   44
  7  \w     88.00 177.00   1.00   16.00    --  111.00  30.00 -60.00   89
  8  \w    147.00 173.00   1.00   16.00    --  111.00  61.00   0.00   26
  9  \w    120.00 153.00   1.00   16.00    --  111.00 -15.00  60.00   33
 10  \w    133.00 161.00   1.00   16.00    --  111.00  45.00 150.00   28
 11  \w     91.00 123.00   1.00   16.00    --  111.00  45.00 150.00   32
 12  \w     88.00 144.00   1.00   16.00    --  111.00  61.00   0.00   56
 13  \w     52.00  91.00   1.00   16.00    --  111.00 -30.00-120.00   39
 14  \w     67.00 100.00   1.00   16.00    --  111.00 -77.00-120.00   33
 15  \w     47.00  96.00   1.00   16.00    --  111.00 -45.00-180.00   49
 16  \w     43.00  90.00   1.00   16.00    --  111.00 -45.00-120.00   47
 17  \w     41.00  84.00   1.00   16.00    --  111.00 -45.00  30.00   43
 18  \w     72.00 101.00   1.00   16.00    --  111.00 -94.00  60.00   29
 19  \w     40.00  99.00   1.00   16.00    --  111.00 -45.00 120.00   59
 20  \w     40.00  65.00   1.00   16.00    --  111.00 -15.00  60.00   25
 21  \w     31.00  56.00   1.00   16.00    --  111.00 -94.00  60.00   25
;
_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      0.0661086000
_diffrn_orient_matrix_UB_12      0.0237071000
_diffrn_orient_matrix_UB_13      0.0166331000
_diffrn_orient_matrix_UB_21      0.0248866000
_diffrn_orient_matrix_UB_22      -0.0312436000
_diffrn_orient_matrix_UB_23      0.0515943000
_diffrn_orient_matrix_UB_31      0.0356148000
_diffrn_orient_matrix_UB_32      -0.0221163000
_diffrn_orient_matrix_UB_33      -0.0549341000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -42
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            81469
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.243
_diffrn_reflns_theta_min         3.525
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.482
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83543
_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    1.489
_exptl_crystal_description       needle
_exptl_crystal_F_000             6096
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.899
_refine_diff_density_min         -0.579
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1892
_refine_ls_number_reflns         27584
_refine_ls_number_restraints     828
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0519
_refine_ls_R_factor_gt           0.0393
_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^)+(0.0538P)^2^+8.3149P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0991
_refine_ls_wR_factor_ref         0.1070
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22341
_reflns_number_total             27584
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09364_si_002.cif
_cod_data_source_block           2-NBD
_cod_database_code               4133293
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C56 H64 Rh1 P2 F24 B1'
_shelx_estimated_absorpt_t_max   0.768
_shelx_estimated_absorpt_t_min   0.465
_reflns_odcompleteness_completeness 99.60
_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
 F9-F7 \\sim F9-F8 \\sim F7-F8 \\sim F8A-F7A \\sim F8A-F9A \\sim F7A-F9A
 with sigma of 0.04
 C48-F9 \\sim C48-F7 \\sim C48-F8 \\sim C48-F8A \\sim C48-F7A \\sim C48-F9A
 with sigma of 0.02
 F46-F48 \\sim F46-F47 \\sim F48-F47 \\sim F48A-F47A \\sim F48A-F46A \\sim
F47A-F46A
 with sigma of 0.04
 C130-F46 \\sim C130-F48 \\sim C130-F47 \\sim C130-F48A \\sim C130-F47A \\sim
C130-F46A
 with sigma of 0.02
 F12-F10 \\sim F12-F11 \\sim F10-F11 \\sim F10A-F12A \\sim F10A-F11A \\sim
F12A-F11A
 with sigma of 0.04
 C49-F12 \\sim C49-F10 \\sim C49-F11 \\sim C49-F10A \\sim C49-F12A \\sim
C49-F11A
 with sigma of 0.02
 F1-F3 \\sim F1-F2 \\sim F3-F2 \\sim F3A-F1A \\sim F3A-F2A \\sim F1A-F2A
 with sigma of 0.04
 C41-F1 \\sim C41-F3 \\sim C41-F2 \\sim C41-F3A \\sim C41-F1A \\sim C41-F2A
 with sigma of 0.02
 F44-F45 \\sim F44-F43 \\sim F45-F43 \\sim F45A-F44A \\sim F45A-F43A \\sim
F44A-F43A
 with sigma of 0.04
 C129-F44 \\sim C129-F45 \\sim C129-F43 \\sim C129-F45A \\sim C129-F44A \\sim
C129-F43A
 with sigma of 0.02
 F37-F39 \\sim F37-F38 \\sim F39-F38 \\sim F37A-F39A \\sim F37A-F38A \\sim
F39A-F38A
 with sigma of 0.04
 C121-F37 \\sim C121-F39 \\sim C121-F38 \\sim C121-F37A \\sim C121-F39A \\sim
C121-F38A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C48 \\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
C130 \\sim F46 \\sim F47 \\sim F48 \\sim F46A \\sim F47A \\sim F48A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
C49 \\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
C41 \\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
C129 \\sim F43 \\sim F44 \\sim F45 \\sim F43A \\sim F44A \\sim F45A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C121 \\sim F37 \\sim F38 \\sim F39 \\sim F37A \\sim F38A \\sim F39A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C48, F7, F8, F9, F7A, F8A, F9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C130, F46, F47, F48, F46A, F47A, F48A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C49, F10, F11, F12, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, F1, F2, F3, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C129, F43, F44, F45, F43A, F44A, F45A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C121, F37, F38, F39, F37A, F38A, F39A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F37A)=Sof(F38A)=Sof(F39A)=1-FVAR(1)
 Sof(F37)=Sof(F38)=Sof(F39)=FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(2)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(2)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(3)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(3)
 Sof(F43A)=Sof(F44A)=Sof(F45A)=1-FVAR(4)
 Sof(F43)=Sof(F44)=Sof(F45)=FVAR(4)
 Sof(F46A)=Sof(F47A)=Sof(F48A)=1-FVAR(5)
 Sof(F46)=Sof(F47)=Sof(F48)=FVAR(5)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(6)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C3(H3), C6(H6), C11(H11), C17(H17), C23(H23), C29(H29), C68(H68), C71(H71),
 C76(H76), C82(H82), C88(H88), C93(H93)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C12(H12A,H12B),
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C18(H18A,H18B),
  C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C24(H24A,
 H24B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B),
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B),
  C04S(H04A,H04B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,
 H75B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B),
 C81(H81A,H81B), C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B),
  C87(H87A,H87B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,
 H92B), C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B),
 C98(H98A,H98B)
6.c Aromatic/amide H refined with riding coordinates:
 C01S(H01S), C36(H36), C38(H38), C40(H40), C45(H45), C47(H47), C51(H51),
 C53(H53), C55(H55), C59(H59), C61(H61), C63(H63), C100(H100), C102(H102),
 C104(H104), C108(H108), C110(H110), C112(H112), C116(H116), C118(H118),
 C120(H120), C124(H124), C126(H126), C128(H128)
;
_shelx_res_checksum              9710
_shelx_hkl_checksum              73747
_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 1.221
_oxdiff_exptl_absorpt_empirical_full_min 0.780