MicroED characterization of a robust cationic σ-alkane complex stabilized by the [B(3,5-(SF5)2C6H3)4]− anion, via on-grid solid/gas single-crystal to single-crystal reactivity
Doyle, Laurence R.; Thompson, Emily A.; Burnage, Arron L.; Whitwood, Adrian C.; Jenkins, Huw T.; Macgregor, Stuart A.; Weller, Andrew S.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00335J

data_7709482
_publ_section_title
;
 MicroED characterization of a robust cationic \s-alkane complex
 stabilized by the [B(3,5-(SF5)2C6H3)4]&#x2212; anion, via on-grid
 solid/gas single-crystal to single-crystal reactivity
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00335J
_journal_year                    2022
_chemical_formula_moiety         'C30 H52 P2 Rh, C24 H12 B F40 S8'
_chemical_formula_sum            'C54 H64 B F40 P2 Rh S8'
_chemical_formula_weight         1905.19
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-12-03
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2021-12-07 deposited with the CCDC.	2022-02-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.333(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.5254(8)
_cell_length_b                   18.4417(19)
_cell_length_c                   20.4850(10)
_cell_measurement_reflns_used    2499
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      68.9120
_cell_measurement_theta_min      4.4940
_cell_volume                     7370.2(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      110(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1450
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.972
_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    -25.00  10.00   1.00    7.50    --    0.00  77.00  30.00   35
  2  \w     -5.00  42.00   1.00    7.50    --    0.00  77.00  90.00   47
  3  \w    -20.00   8.00   1.00    7.50    --    0.00 -77.00 -90.00   28
  4  \w    -14.00  56.00   1.00   30.00    --   54.00 -57.00-120.00   70
  5  \w     29.00 105.00   1.00   30.00    --   54.00-125.00-180.00   76
  6  \w     27.00  53.00   1.00   30.00    --   54.00-125.00  60.00   26
  7  \w      4.00 121.00   1.00   30.00    --   54.00   0.00-120.00  117
  8  \w    108.00 173.00   1.00  120.00    --  108.00  77.00-180.00   65
  9  \w    103.00 171.00   1.00  120.00    --  108.00  77.00 -90.00   68
 10  \w    103.00 142.00   1.00  120.00    --  108.00  77.00  60.00   39
 11  \w     46.00  98.00   1.00  120.00    --  108.00 -91.00  60.00   52
 12  \w    103.00 165.00   1.00  120.00    --  108.00  77.00 -30.00   62
 13  \w    108.00 138.00   1.00  120.00    --  108.00 111.00  30.00   30
 14  \w     61.00 146.00   1.00  120.00    --  108.00 178.00  60.00   85
 15  \w     40.00 107.00   1.00  120.00    --  108.00 -91.00-180.00   67
 16  \w    150.00 177.00   1.00  120.00    --  108.00 111.00  30.00   27
 17  \w     44.00 104.00   1.00  120.00    --  108.00-111.00  30.00   60
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0166080000
_diffrn_orient_matrix_UB_12      -0.0542843000
_diffrn_orient_matrix_UB_13      0.0543466000
_diffrn_orient_matrix_UB_21      -0.0096431000
_diffrn_orient_matrix_UB_22      -0.0603526000
_diffrn_orient_matrix_UB_23      -0.0514220000
_diffrn_orient_matrix_UB_31      0.0766688000
_diffrn_orient_matrix_UB_32      -0.0192928000
_diffrn_orient_matrix_UB_33      0.0083898000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0431
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            13346
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.788
_diffrn_reflns_theta_min         3.892
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.681
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.559
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.717
_exptl_crystal_description       block
_exptl_crystal_F_000             3824
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.214
_exptl_crystal_size_min          0.117
_refine_diff_density_max         1.577
_refine_diff_density_min         -0.635
_refine_diff_density_rms         0.152
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     648
_refine_ls_number_reflns         6905
_refine_ls_number_restraints     858
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1319
_refine_ls_R_factor_gt           0.0946
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1070P)^2^+62.9053P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2460
_refine_ls_wR_factor_ref         0.2755
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4573
_reflns_number_total             6905
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00335j2.cif
_cod_data_source_block           asw21028
_cod_database_code               7709482
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C54 H68 B S8 F40 P2 Rh'
_chemical_oxdiff_usercomment     LD48N
_shelx_estimated_absorpt_t_max   0.556
_shelx_estimated_absorpt_t_min   0.368
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 S4-C26 \\sim S3-C24 \\sim S1A-C18 \\sim S1-C18 \\sim S2A-C20 \\sim S2-C20
 with sigma of 0.02
 C2-C1 \\sim C1A-C2A
 with sigma of 0.02
 S4-F18 \\sim S4-F17 \\sim S4-F16 \\sim S4-F19 \\sim S3-F14 \\sim S3-F13 \\sim
S3-F11 \\sim S3-F12 \\sim S1A-
 F3A \\sim S1-F3 \\sim S1A-F2A \\sim S1-F2 \\sim S1-F1 \\sim S1A-F1A \\sim
S1-F4 \\sim S1A-F4A \\sim S2-F7 ~
 S2A-F7A \\sim S2A-F8A \\sim S2-F8 \\sim S2A-F9A \\sim S2-F9 \\sim S2-F6 \\sim
S2A-F6A
 with sigma of 0.02
 S3-F15 \\sim S4-F20 \\sim S2-F10 \\sim S2A-F10A \\sim S1A-F5A \\sim S1-F5
 with sigma of 0.02
 Rh1-C2 \\sim Rh1-C1 \\sim Rh1A-C2A \\sim Rh1A-C1A
 with sigma of 0.02
 C12A-C11A \\sim C12-C11 \\sim C14-C15 \\sim C14A-C15A \\sim C6-C5 \\sim C9-C8
 with sigma of 0.02
 P1-C4 \\sim P1-C10
 with sigma of 0.02
 C6-C7 \\sim C8-C7 \\sim C13A-C14A \\sim C12A-C13A \\sim C14-C13 \\sim C12-C13
 with sigma of 0.02
 C9-C4 \\sim C4-C5 \\sim C15A-C10 \\sim C15-C10 \\sim C11A-C10 \\sim C11-C10
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S2 \\sim S2A \\sim F6 \\sim F6A \\sim F7 \\sim F7A \\sim F8 \\sim F8A \\sim F9
\\sim F9A \\sim F10 \\sim F10A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
S1A \\sim S1 \\sim F1A \\sim F1 \\sim F2A \\sim F2 \\sim F3A \\sim F3 \\sim F4A
\\sim F4 \\sim F5A \\sim F5: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C1 \\sim C2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C1A \\sim C2A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C10 \\sim C11 \\sim C11A \\sim C12 \\sim C12A \\sim C13 \\sim C13A \\sim C14
\\sim C14A \\sim C15 \\sim C15A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
4. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(S2A)=Sof(F6A)=
 Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=1-FVAR(1)
 Sof(Rh1A)=0.5*(1-FVAR(2))
 Sof(Rh1)=0.5*FVAR(2)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(S2)=Sof(F6)=Sof(F7)=
 Sof(F8)=Sof(F9)=Sof(F10)=FVAR(1)
 Sof(S1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=1-FVAR(2)
 Sof(S1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=FVAR(2)
 Sof(H10A)=Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=Sof(H12D)=
 Sof(C13A)=Sof(H13C)=Sof(H13D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(C15A)=
 Sof(H15C)=Sof(H15D)=1-FVAR(3)
 Sof(H10)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=
 Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 FVAR(3)
5.a Riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB), C2(H2A,H2B), C2A(H2AA,H2AB)
5.b Ternary CH refined with riding coordinates:
 C4(H4), C10(H10), C10(H10A)
5.c Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C11(H11A,
 H11B), C11A(H11C,H11D), C12(H12A,H12B), C12A(H12C,H12D), C13(H13A,H13B),
 C13A(H13C,H13D), C14(H14A,H14B), C14A(H14C,H14D), C15(H15A,H15B), C15A(H15C,
 H15D)
5.d Aromatic/amide H refined with riding coordinates:
 C17(H17), C19(H19), C21(H21), C23(H23), C25(H25), C27(H27)
;
_shelx_res_checksum              24749
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.484
_oxdiff_exptl_absorpt_empirical_full_min 0.587