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_4133299
_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         'C36 H64 P2 Rh, C32 H12 B F24'
_chemical_formula_sum            'C68 H76 B F24 P2 Rh'
_chemical_formula_weight         1524.94
_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   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                 94.0465(18)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.7070(4)
_cell_length_b                   34.3875(8)
_cell_length_c                   20.3368(4)
_cell_measurement_reflns_used    16612
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.2680
_cell_measurement_theta_min      4.2820
_cell_volume                     13747.4(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43b (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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -41.00   4.00   1.00    4.00    --  -41.77  37.00 -30.00   45
  2  \w    -93.00 -55.00   1.00    4.00    --  -41.77 125.00  90.00   38
  3  \w    -45.00  31.00   1.00    4.00    --  -41.77  37.00  90.00   76
  4  \w     16.00 100.00   1.00    4.00    --   41.77  57.00   0.00   84
  5  \w     72.00  97.00   1.00   16.00    --  111.00 -77.00 -60.00   25
  6  \w    114.00 141.00   1.00   16.00    --  111.00 -77.00 -60.00   27
  7  \w     41.00  98.00   1.00   16.00    --  111.00 -45.00-180.00   57
  8  \w     46.00  72.00   1.00   16.00    --  111.00 -30.00-180.00   26
  9  \w     55.00 114.00   1.00   16.00    --  111.00-111.00 -30.00   59
 10  \w     99.00 140.00   1.00   16.00    --  111.00-158.00 162.00   41
 11  \w     62.00 103.00   1.00   16.00    --  111.00-118.00 -43.00   41
 12  \w     36.00  83.00   1.00   16.00    --  111.00 -30.00 120.00   47
 13  \w     50.00  96.00   1.00   16.00    --  111.00 -45.00   0.00   46
 14  \w    109.00 176.00   1.00   16.00    --  111.00  30.00  60.00   67
 15  \w     73.00  98.00   1.00   16.00    --  111.00 -45.00-120.00   25
 16  \w    105.00 178.00   1.00   16.00    --  111.00  30.00 -60.00   73
 17  \w     46.00  84.00   1.00   16.00    --  111.00 -45.00  90.00   38
 18  \w     39.00 100.00   1.00   16.00    --  111.00 -94.00   0.00   61
 19  \w    104.00 157.00   1.00   16.00    --  111.00 111.00 120.00   53
 20  \w     38.00  69.00   1.00   16.00    --  111.00 -94.00  30.00   31
 21  \w     51.00  91.00   1.00   16.00    --  111.00 -30.00  30.00   40
;
_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      0.0049745000
_diffrn_orient_matrix_UB_12      -0.0443494000
_diffrn_orient_matrix_UB_13      -0.0089350000
_diffrn_orient_matrix_UB_21      -0.0660548000
_diffrn_orient_matrix_UB_22      0.0005455000
_diffrn_orient_matrix_UB_23      -0.0453044000
_diffrn_orient_matrix_UB_31      0.0418970000
_diffrn_orient_matrix_UB_32      0.0062451000
_diffrn_orient_matrix_UB_33      -0.0603306000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0561
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            26180
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.075
_diffrn_reflns_theta_min         3.965
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.388
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66246
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43b (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    1.474
_exptl_crystal_description       prism
_exptl_crystal_F_000             6240
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         2.321
_refine_diff_density_min         -1.815
_refine_diff_density_rms         0.143
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.938
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1923
_refine_ls_number_reflns         26180
_refine_ls_number_restraints     999
_refine_ls_restrained_S_all      0.950
_refine_ls_R_factor_all          0.1170
_refine_ls_R_factor_gt           0.0834
_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^)+(0.1589P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2148
_refine_ls_wR_factor_ref         0.2329
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14936
_reflns_number_total             26180
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09364_si_002.cif
_cod_data_source_block           3-COD
_cod_database_code               4133299
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C68 H76 B1 F24 Rh P2'
_shelx_estimated_absorpt_t_max   0.648
_shelx_estimated_absorpt_t_min   0.581
_reflns_odcompleteness_completeness 99.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.560(16)
 0.440(16)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 F1-F2 \\sim F1-F3 \\sim F2-F3 \\sim F2A-F1A \\sim F2A-F3A \\sim F1A-F3A
 with sigma of 0.04
 F10-F11 \\sim F10-F12 \\sim F11-F12 \\sim F11A-F12A \\sim F11A-F10A \\sim
F12A-F10A
 with sigma of 0.04
 F25-F26 \\sim F25-F27 \\sim F26-F27 \\sim F25A-F27A \\sim F25A-F26A \\sim
F27A-F26A
 with sigma of 0.04
 F34-F35 \\sim F34-F36 \\sim F35-F36 \\sim F34A-F36A \\sim F34A-F35A \\sim
F36A-F35A \\sim F35B-F36B ~
 F35B-F34B \\sim F36B-F34B
 with sigma of 0.04
 P4-C92 \\sim P4A-C92A
 with sigma of 0.02
 C43-F1 \\sim C43-F2 \\sim C43-F3 \\sim C43-F2A \\sim C43-F1A \\sim C43-F3A
 with sigma of 0.01
 C52-F10 \\sim C52-F11 \\sim C52-F12 \\sim C52-F11A \\sim C52-F12A \\sim
C52-F10A
 with sigma of 0.01
 C111-F25 \\sim C111-F26 \\sim C111-F27 \\sim C111-F25A \\sim C111-F27A \\sim
C111-F26A
 with sigma of 0.01
 C120-F34 \\sim C120-F35 \\sim C120-F36 \\sim C120-F34A \\sim C120-F36A \\sim
C120-F35A \\sim C120-
 F35B \\sim C120-F36B \\sim C120-F34B
 with sigma of 0.01
 Rh2-P4 \\sim Rh2A-P4A \\sim Rh2-P3 \\sim Rh2A-P4B
 with sigma of 0.02
 C92A-C91A \\sim C92-C91 \\sim C91A-C90A \\sim C91-C90 \\sim C90A-C89A \\sim
C90-C89
 with sigma of 0.02
 P3-C89 \\sim P4B-C89A
 with sigma of 0.02
 P4B-C83 \\sim P4B-C77 \\sim P3-C77 \\sim P3-C83
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C43 \\sim F1 \\sim F2 \\sim F3 \\sim F2A \\sim F1A \\sim F3A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
C52 \\sim F10 \\sim F11 \\sim F12 \\sim F11A \\sim F12A \\sim F10A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C111 \\sim F25 \\sim F26 \\sim F27 \\sim F25A \\sim F27A \\sim F26A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.01
C120 \\sim F34 \\sim F35 \\sim F36 \\sim F34A \\sim F36A \\sim F35A \\sim F35B
\\sim F36B \\sim F34B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.01
C92 \\sim C91 \\sim C90 \\sim C89 \\sim P3: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.01
C84 \\sim P3 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim P4B \\sim P4A \\sim
C90A \\sim C89A \\sim C91A \\sim C92A \\sim P4: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.01
Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F36A) \\sim Ueq, Uanis(F36B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F36) \\sim Ueq, Uanis(F36A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F35) \\sim Ueq, Uanis(F35A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F35) \\sim Ueq, Uanis(F35B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F36A) = Uanis(F36B)
Uanis(Rh2) = Uanis(Rh2A)
5. Rigid body (RIGU) restrains
 C43, F1, F2, F3, F2A, F1A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C52, F10, F11, F12, F11A, F12A, F10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C111, F25, F26, F27, F25A, F27A, F26A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C120, F34, F35, F36, F34A, F36A, F35A, F35B, F36B, F34B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P4, C92, C91, C90, C89, P3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Rh2A, Rh2, P3, P4B, P4A, P4, C92, C90A, C90, C89, C89A, C91A, C91, C92A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(F34)+Sof(F35)+Sof(F36)]+1*[Sof(F34A)+Sof(F36A)+Sof(F35A)]+1*[Sof(F35B)+
 Sof(F36B)+Sof(F34B)]=1 with esd of 0.0001
 Sof(F2A)=Sof(F1A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(F11A)=Sof(F12A)=Sof(F10A)=1-FVAR(2)
 Sof(F10)=Sof(F11)=Sof(F12)=FVAR(2)
 Sof(F25A)=Sof(F27A)=Sof(F26A)=1-FVAR(3)
 Sof(F25)=Sof(F26)=Sof(F27)=FVAR(3)
 Sof(F34)=Sof(F35)=Sof(F36)=FVAR(4)
 Sof(F34A)=Sof(F36A)=Sof(F35A)=FVAR(5)
 Sof(F35B)=Sof(F36B)=Sof(F34B)=FVAR(6)
 Sof(Rh2A)=Sof(P4B)=Sof(P4A)=Sof(C90A)=Sof(H90C)=Sof(H90D)=Sof(C89A)=Sof(H89C)=
 Sof(H89D)=Sof(C91A)=Sof(H91C)=Sof(H91D)=Sof(C92A)=Sof(H92C)=Sof(H92D)=1-FVAR(7)
 Sof(Rh2)=Sof(P3)=Sof(P4)=Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(C90)=Sof(H90A)=
 Sof(H90B)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(C92)=Sof(H92A)=Sof(H92B)=FVAR(7)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6), C9(H9), C15(H15), C25(H25), C31(H31),
 C69(H69), C70(H70), C73(H73), C74(H74), C77(H77), C83(H83), C93(H93), C99(H99)
7.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B), C10(H10K,H10L), C11(H11A,
 H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C16(H16A,H16B),
 C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B),
  C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C26(H26A,H26B), C27(H27A,
 H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C32(H32A,H32B),
 C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C71(H71A,H71B),
  C72(H72A,H72B), C75(H75A,H75B), C76(H76A,H76B), C78(H78A,H78B), C79(H79A,
 H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C84(H84A,H84B),
 C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B), C94(H94A,H94B),
  C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B), C98(H98A,H98B), C100(H10A,
 H10B), C101(H10C,H10D), C102(H10E,H10F), C103(H10G,H10H), C104(H10I,H10J),
 C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B), C90A(H90C,
 H90D), C89A(H89C,H89D), C91A(H91C,H91D), C92A(H92C,H92D)
7.c Aromatic/amide H refined with riding coordinates:
 C38(H38), C40(H40), C42(H42), C46(H46), C48(H48), C50(H50), C54(H54),
 C56(H56), C58(H58), C62(H62), C64(H64), C66(H66), C106(H106), C108(H108),
 C110(H110), C114(H114), C116(H116), C118(H118), C122(H122), C124(H124),
 C126(H126), C130(H130), C132(H132), C134(H134)
;
_shelx_res_checksum              23141
_shelx_hkl_checksum              16053
_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 1.461
_oxdiff_exptl_absorpt_empirical_full_min 0.589