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_4133301
_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
'2(C36 H65 P2 Rh0.95), 2(C32 H12 B F24), 0.05(Rh)'
_chemical_formula_sum            'C136 H154 B2 F48 P4 Rh2'
_chemical_formula_weight         3051.90
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 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                 94.612(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.6397(7)
_cell_length_b                   17.8000(5)
_cell_length_c                   77.042(2)
_cell_measurement_reflns_used    9341
_cell_measurement_temperature    150
_cell_measurement_theta_max      25.5500
_cell_measurement_theta_min      1.8360
_cell_volume                     28212.6(14)
_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_temperature      150.0
_diffrn_detector_area_resol_mean 0.0350
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_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   -104.00  16.00   0.20    0.20    --   28.00  60.00 -80.00  600
  2  \f    -80.00  40.00   0.20    0.20  16.00  28.00  60.00    --   600
  3  \w   -104.00  16.00   0.20    0.20    --   28.00  60.00  40.00  600
  4  \f     40.00 160.00   0.20    0.20  16.00  28.00  60.00    --   600
  5  \w   -104.00  16.00   0.20    0.20    --   28.00  60.00 160.00  600
  6  \f    -90.00  90.00   0.20    0.20  16.00  28.00   0.00    --   900
;
_diffrn_measurement_device       'CrystalLogic Kappa (4 circle)'
_diffrn_measurement_device_type  'Kappa Rigaku Saturn724+'
_diffrn_measurement_method       'omega rotation'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.0940
_diffrn_reflns_av_unetI/netI     0.0916
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       85
_diffrn_reflns_limit_l_min       -76
_diffrn_reflns_number            94644
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        22.502
_diffrn_reflns_theta_max         22.502
_diffrn_reflns_theta_min         1.697
_exptl_absorpt_coefficient_mu    0.362
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38859
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.437
_exptl_crystal_description       block
_exptl_crystal_F_000             12496
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         6.213
_refine_diff_density_min         -1.158
_refine_diff_density_rms         0.196
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.459
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2011
_refine_ls_number_reflns         19997
_refine_ls_number_restraints     5073
_refine_ls_restrained_S_all      1.381
_refine_ls_R_factor_all          0.2238
_refine_ls_R_factor_gt           0.1580
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3934
_refine_ls_wR_factor_ref         0.4456
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10176
_reflns_number_total             19997
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09364_si_002.cif
_cod_data_source_block           4-NBA
_cod_original_cell_volume        28212.6(15)
_cod_database_code               4133301
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.965
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Rh2A-Rh2
 1.75 with sigma of 0.02
 C20-C21 \\sim C21-C22 \\sim C22-C23 \\sim C23-C24 \\sim C24-C19 \\sim C19-C20
 with sigma of 0.02
 C20-C24 \\sim C22-C24 \\sim C21-C19 \\sim C21-C23 \\sim C23-C19 \\sim C20-C22
 with sigma of 0.04
 C52-F11 \\sim C52-F12 \\sim C52-F10
 with sigma of 0.02
 C44-F5 \\sim C44-F4 \\sim C44-F6
 with sigma of 0.02
 C44A-F29 \\sim C44A-F30 \\sim C44A-F28
 with sigma of 0.02
 C43A-F27 \\sim C43A-F25 \\sim C43A-F26
 with sigma of 0.02
 C67A-F43 \\sim C67A-F44 \\sim C67A-F45
 with sigma of 0.02
 C68A-F46 \\sim C68A-F47 \\sim C68A-F48
 with sigma of 0.02
 C51A-F31 \\sim C51A-F32 \\sim C51A-F33
 with sigma of 0.02
 C52A-F36 \\sim C52A-F34 \\sim C52A-F35
 with sigma of 0.02
 F4-F5 \\sim F4-F6 \\sim F5-F6
 with sigma of 0.04
 F10-F11 \\sim F10-F12 \\sim F11-F12
 with sigma of 0.04
 F25-F26 \\sim F25-F27 \\sim F26-F27
 with sigma of 0.04
 F28-F29 \\sim F28-F30 \\sim F29-F30
 with sigma of 0.04
 F31-F32 \\sim F31-F33 \\sim F32-F33
 with sigma of 0.04
 F34-F35 \\sim F34-F36 \\sim F35-F36
 with sigma of 0.04
 F43-F44 \\sim F43-F45 \\sim F44-F45
 with sigma of 0.04
 F46-F47 \\sim F46-F48 \\sim F47-F48
 with sigma of 0.04
 C59-F15 \\sim C59-F13 \\sim C59-F14 \\sim C59-F15A \\sim C59-F13A \\sim
C59-F14A
 with sigma of 0.02
 F13-F14 \\sim F13-F15 \\sim F14-F15 \\sim F13A-F14A \\sim F13A-F15A \\sim
F14A-F15A
 with sigma of 0.04
 C60-F16 \\sim C60-F18 \\sim C60-F17 \\sim C60-F16A \\sim C60-F18A \\sim
C60-F17A
 with sigma of 0.02
 F16-F17 \\sim F16-F18 \\sim F17-F18 \\sim F16A-F17A \\sim F16A-F18A \\sim
F17A-F18A
 with sigma of 0.04
 C67-F21 \\sim C67-F19 \\sim C67-F20 \\sim C67-F21A \\sim C67-F19A \\sim
C67-F20A
 with sigma of 0.02
 F19-F20 \\sim F19-F21 \\sim F20-F21 \\sim F19A-F20A \\sim F19A-F21A \\sim
F20A-F21A
 with sigma of 0.04
 C59A-F39 \\sim C59A-F37 \\sim C59A-F38 \\sim C59A-F39A \\sim C59A-F37A \\sim
C59A-F38A
 with sigma of 0.02
 F37-F38 \\sim F37-F39 \\sim F38-F39 \\sim F37A-F38A \\sim F37A-F39A \\sim
F38A-F39A
 with sigma of 0.04
 C60A-F42 \\sim C60A-F41 \\sim C60A-F40 \\sim C60A-F42A \\sim C60A-F41A \\sim
C60A-F40A
 with sigma of 0.02
 F40-F41 \\sim F40-F42 \\sim F41-F42 \\sim F40A-F41A \\sim F40A-F42A \\sim
F41A-F42A
 with sigma of 0.04
 C43-F2 \\sim C43-F3 \\sim C43-F1 \\sim C43-F2A \\sim C43-F3A \\sim C43-F1A
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F1A-F2A \\sim F1A-F3A \\sim F2A-F3A
 with sigma of 0.04
 C68-F24 \\sim C68-F23 \\sim C68-F22 \\sim C68-F24A \\sim C68-F23A \\sim
C68-F22A
 with sigma of 0.02
 F22-F23 \\sim F22-F24 \\sim F23-F24 \\sim F22A-F23A \\sim F22A-F24A \\sim
F23A-F24A
 with sigma of 0.04
 F9-C51 \\sim F7-C51 \\sim F8-C51 \\sim F9A-C51 \\sim F7A-C51 \\sim F8A-C51
 with sigma of 0.02
 F7-F8 \\sim F7-F9 \\sim F8-F9 \\sim F7A-F8A \\sim F7A-F9A \\sim F8A-F9A
 with sigma of 0.02
 C3C-C4C \\sim C3C-C2C \\sim C4C-C5C \\sim C2C-C1C \\sim C5C-C6C \\sim C1C-C6C
\\sim C3C-C7C \\sim C7C-C6C
 with sigma of 0.02
 C3B-C4B \\sim C3B-C2B \\sim C4B-C5B \\sim C2B-C1B \\sim C5B-C6B \\sim C1B-C6B
\\sim C3B-C7B \\sim C7B-C6B
 with sigma of 0.02
 C3A-C4A \\sim C3A-C2A \\sim C4A-C5A \\sim C2A-C1A \\sim C5A-C6A \\sim C1A-C6A
\\sim C3A-C7A \\sim C7A-C6A
 with sigma of 0.02
 C3-C2 \\sim C3-C4 \\sim C2-C1 \\sim C4-C5 \\sim C1-C6 \\sim C5-C6 \\sim C3-C7
\\sim C7-C6
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(Rh2) = Uanis(Rh2A)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F15A)=Sof(F14A)=Sof(F13A)=1-FVAR(1)
 Sof(F15)=Sof(F13)=Sof(F14)=FVAR(1)
 Sof(F38A)=Sof(F37A)=Sof(F39A)=1-FVAR(2)
 Sof(F39)=Sof(F37)=Sof(F38)=FVAR(2)
 Sof(F40A)=Sof(F41A)=Sof(F42A)=1-FVAR(3)
 Sof(F42)=Sof(F41)=Sof(F40)=FVAR(3)
 Sof(F2A)=Sof(F3A)=Sof(F1A)=1-FVAR(4)
 Sof(F2)=Sof(F3)=Sof(F1)=FVAR(4)
 Sof(F22A)=Sof(F24A)=Sof(F23A)=1-FVAR(5)
 Sof(F24)=Sof(F23)=Sof(F22)=FVAR(5)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(6)
 Sof(F9)=Sof(F7)=Sof(F8)=FVAR(6)
 Sof(Rh2A)=1-FVAR(7)
 Sof(Rh2)=FVAR(7)
 Sof(C3)=Sof(H3)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=
 Sof(H6)=1-FVAR(8)
 Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C1A)=Sof(H1AA)=
 Sof(H1AB)=Sof(C6A)=Sof(H6A)=FVAR(8)
 Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=
 Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(C1B)=Sof(H1BA)=
 Sof(H1BB)=Sof(C6B)=Sof(H6B)=1-FVAR(9)
 Sof(C3C)=Sof(H3C)=Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(C2C)=Sof(H2CA)=Sof(H2CB)=
 Sof(C7C)=Sof(H7CA)=Sof(H7CB)=Sof(C5C)=Sof(H5CA)=Sof(H5CB)=Sof(C1C)=Sof(H1CA)=
 Sof(H1CB)=Sof(C6C)=Sof(H6C)=FVAR(9)
 Fixed Sof: F21(0.5) F16(0.5) F18(0.5) F19(0.5) F20(0.5) F17(0.5) F18A(0.5)
 F17A(0.5) F16A(0.5) F19A(0.5) F20A(0.5) F21A(0.5)
7.a Free rotating group:
 C20(C21,C22,C23,C24,C19), C3(C2,C4,C7,C1,C5,C6), C3C(C4C,C2C,C7C,C5C,C1C,C6C),
  C3A(C4A,C2A,C7A,C5A,C1A,C6A), C3B(C4B,C2B,C7B,C5B,C1B,C6B)
7.b Ternary CH refined with riding coordinates:
 C25(H25), C10A(H10A), C10(H10), C25A(H25A), C13(H13), C13A(H13A), C31(H31),
 C31A(H31A), C19A(H19A), C19(H19), C3(H3), C6(H6), C3C(H3C), C6C(H6C), C3A(H3A),
  C6A(H6A), C3B(H3B), C6B(H6B)
7.c Secondary CH2 refined with riding coordinates:
 C12A(H12A,H12B), C16A(H16A,H16B), C11(H11C,H11D), C14A(H14A,H14B), C11A(H11A,
 H11B), C9(H9A,H9B), C32A(H32A,H32B), C9A(H9AA,H9AB), C14(H14C,H14D), C36(H36C,
 H36D), C15A(H15A,H15B), C34A(H34A,H34B), C30A(H30A,H30B), C29A(H29A,H29B),
 C30(H30C,H30D), C26A(H26A,H26B), C29(H29C,H29D), C34(H34C,H34D), C16(H16C,
 H16D), C22A(H22A,H22B), C28(H28C,H28D), C27A(H27A,H27B), C28A(H28A,H28B),
 C17A(H17A,H17B), C15(H15C,H15D), C36A(H36A,H36B), C35(H35C,H35D), C18(H18C,
 H18D), C33A(H33A,H33B), C17(H17C,H17D), C18A(H18A,H18B), C35A(H35A,H35B),
 C24A(H24A,H24B), C27(H27C,H27D), C8A(H8AA,H8AB), C33(H33C,H33D), C21A(H21A,
 H21B), C20A(H20A,H20B), C26(H26C,H26D), C12(H12C,H12D), C23A(H23A,H23B),
 C32(H32C,H32D), C8(H8A,H8B), C20(H20C,H20D), C21(H21C,H21D), C22(H22C,H22D),
 C23(H23C,H23D), C24(H24C,H24D), C2(H2A,H2B), C4(H4A,H4B), C7(H7A,H7B), C1(H1A,
 H1B), C5(H5A,H5B), C4C(H4CA,H4CB), C2C(H2CA,H2CB), C7C(H7CA,H7CB), C5C(H5CA,
 H5CB), C1C(H1CA,H1CB), C4A(H4AA,H4AB), C2A(H2AA,H2AB), C7A(H7AA,H7AB),
 C5A(H5AA,H5AB), C1A(H1AA,H1AB), C4B(H4BA,H4BB), C2B(H2BA,H2BB), C7B(H7BA,H7BB),
  C5B(H5BA,H5BB), C1B(H1BA,H1BB)
7.d Aromatic/amide H refined with riding coordinates:
 C50(H50), C42A(H42A), C46(H46), C50A(H50A), C38A(H38A), C46A(H46A), C42(H42),
 C66(H66), C54A(H54A), C58A(H58A), C40A(H40A), C38(H38), C48(H48), C62(H62),
 C40(H40), C54(H54), C62A(H62A), C58(H58), C48A(H48A), C66A(H66A), C56(H56),
 C64A(H64A), C56A(H56A), C64(H64)
;
_shelx_res_checksum              60859
_shelx_hkl_checksum              47907
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_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
;