Host guest chemistry of a bidentate silyl-triflate bis-Lewis-acid – complex complexation behaviour unravelled by diffusion NMR spectroscopy
Schäfer, Fabian; Mix, Andreas; Cati, Ninive; Lamm, Jan-Hendrik; Neumann, Beate; Stammler, Georg; Mitzel, Norbert Werner; Dalton Transactions  (2022) –; doi:10.1039/D2DT00583B

data_7710044
_publ_section_title
;
 Host guest chemistry of a bidentate silyl-triflate bis-Lewis-acid --
 complex complexation behaviour unravelled by diffusion NMR spectroscopy
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00583B
_journal_year                    2022
_chemical_formula_moiety         'C40 H68 N4 Si6, 4(C F3 O3 S), 3(C2 H3 N)'
_chemical_formula_sum            'C50 H77 F12 N7 O12 S4 Si6'
_chemical_formula_weight         1492.96
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-22
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2021-04-30 deposited with the CCDC.	2022-04-14 downloaded from the CCDC.
;
_cell_angle_alpha                115.737(4)
_cell_angle_beta                 101.219(4)
_cell_angle_gamma                107.630(4)
_cell_formula_units_Z            1
_cell_length_a                   12.5131(7)
_cell_length_b                   13.0673(6)
_cell_length_c                   13.5178(6)
_cell_measurement_reflns_used    10762
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.3500
_cell_measurement_theta_min      3.8440
_cell_volume                     1755.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3114
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.983
_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   -106.00  -6.00   1.00    3.08    --  -38.05 -57.00 -60.00  100
  2  \w    -47.00  -9.00   1.00    3.08    --  -38.05 -57.00   0.00   38
  3  \w    -53.00 -13.00   1.00    3.08    --  -38.05 -57.00-120.00   40
  4  \w   -127.00 -72.00   1.00    3.08    --  -38.05-178.00 150.00   55
  5  \w   -112.00 -41.00   1.00    3.08    --  -38.05 -57.00 -90.00   71
  6  \w    -91.00  -6.00   1.00    3.08    --  -38.05 -57.00 120.00   85
  7  \w   -114.00 -43.00   1.00    3.08    --  -38.05 178.00 -30.00   71
  8  \w   -127.00  23.00   1.00    3.08    --  -38.05   0.00  30.00  150
  9  \w    -63.00  40.00   1.00    3.08    --  -38.05  38.00-180.00  103
 10  \w   -116.00  -6.00   1.00    3.08    --  -38.05 -57.00  30.00  110
 11  \w    -73.00  -9.00   1.00    3.08    --  -38.05 -38.00 120.00   64
 12  \w   -123.00 -38.00   1.00    3.08    --  -38.05 178.00 -60.00   85
 13  \w    -89.00 -40.00   1.00    3.08    --  -38.05 -38.00  30.00   49
 14  \w   -113.00 -86.00   1.00    3.08    --  -38.05 -57.00   0.00   27
 15  \w   -114.00 -62.00   1.00    3.08    --  -38.05 -57.00-120.00   52
 16  \w      6.00  35.00   1.00    3.08    --   38.05 -99.00   0.00   29
 17  \w     75.00 100.00   1.00    3.08    --   38.05  57.00 -90.00   25
 18  \w      6.00  68.00   1.00    3.08    --   38.05  57.00 -90.00   62
 19  \w     56.00  82.00   1.00    3.08    --   38.05 -99.00   0.00   26
 20  \w     -1.00  26.00   1.00    3.08    --   38.05  89.00 166.72   27
 21  \w     30.00  76.00   1.00    3.08    --   38.05 -99.00-180.00   46
 22  \w     59.00 114.00   1.00    3.08    --   38.05-178.00 -30.00   55
 23  \w     -3.00  23.00   1.00    3.08    --   38.05  92.00  10.34   26
 24  \w     18.00 117.00   1.00    3.08    --   38.05  19.00-150.00   99
 25  \w      3.00  32.00   1.00    3.08    --   38.05  77.00 -72.59   29
 26  \w     79.00 108.00   1.00    3.08    --   38.05 178.00  60.00   29
 27  \w     35.00 108.00   1.00   13.50    --  115.00-111.00 -90.00   73
 28  \w     81.00 110.00   1.00   13.50    --  115.00  62.00  98.48   29
 29  \w     82.00 110.00   1.00   13.50    --  115.00  61.00  60.00   28
 30  \w     82.00 110.00   1.00   13.50    --  115.00  61.00-120.00   28
 31  \w    127.00 175.00   1.00   13.50    --  115.00  61.00  90.00   48
 32  \w     83.00 110.00   1.00   13.50    --  115.00  53.00 141.01   27
 33  \w     84.00 113.00   1.00   13.50    --  115.00  45.00  73.17   29
 34  \w     31.00 106.00   1.00   13.50    --  115.00 -94.00  60.00   75
 35  \w     33.00  93.00   1.00   13.50    --  115.00 -77.00   0.00   60
 36  \w    117.00 178.00   1.00   13.50    --  115.00  66.00 -97.58   61
 37  \w     84.00 111.00   1.00   13.50    --  115.00  45.00   0.00   27
 38  \w     85.00 110.00   1.00   13.50    --  115.00  45.00  60.00   25
 39  \w     80.00 108.00   1.00   13.50    --  115.00  66.00 -97.58   28
 40  \w     84.00 178.00   1.00   13.50    --  115.00  33.00-174.51   94
 41  \w     79.00 107.00   1.00   13.50    --  115.00  65.00 162.43   28
 42  \w    131.00 178.00   1.00   13.50    --  115.00  61.00 120.00   47
 43  \w     29.00 107.00   1.00   13.50    --  115.00 -94.00-180.00   78
 44  \w     83.00 126.00   1.00   13.50    --  115.00  61.00 120.00   43
 45  \w     34.00  86.00   1.00   13.50    --  115.00-111.00-120.00   52
 46  \w     82.00 158.00   1.00   13.50    --  115.00  61.00 -60.00   76
 47  \w    120.00 178.00   1.00   13.50    --  115.00  70.00  62.60   58
 48  \w     80.00 110.00   1.00   13.50    --  115.00  63.00   7.73   30
 49  \w     82.00 112.00   1.00   13.50    --  115.00  61.00-180.00   30
 50  \w     77.00 109.00   1.00   13.50    --  115.00  30.00 -60.00   32
 51  \w     43.00 109.00   1.00   13.50    --  115.00-111.00   0.00   66
 52  \w    108.00 150.00   1.00   13.50    --  115.00 -77.00   0.00   42
 53  \w     85.00 111.00   1.00   13.50    --  115.00  45.00-150.00   26
 54  \w     82.00 117.00   1.00   13.50    --  115.00  61.00  90.00   35
 55  \w     80.00 156.00   1.00   13.50    --  115.00  64.00 -46.28   76
 56  \w     80.00 109.00   1.00   13.50    --  115.00  66.00 136.89   29
 57  \w     80.00 115.00   1.00   13.50    --  115.00  70.00  62.60   35
 58  \w     83.00 157.00   1.00   13.50    --  115.00  52.00   6.04   74
 59  \w     31.00  86.00   1.00   13.50    --  115.00 -77.00 -90.00   55
 60  \w     86.00 115.00   1.00   13.50    --  115.00  45.00-120.00   29
 61  \w    150.00 175.00   1.00   13.50    --  115.00  51.00-147.66   25
 62  \w    134.00 162.00   1.00   13.50    --  115.00  61.00-120.00   28
 63  \w     73.00 107.00   1.00   13.50    --  115.00 -94.00 120.00   34
 64  \w     29.00  58.00   1.00   13.50    --  115.00 -94.00 120.00   29
 65  \w     83.00 120.00   1.00   13.50    --  115.00  51.00-147.66   37
 66  \w     84.00 129.00   1.00   13.50    --  115.00  44.00 101.73   45
 67  \w     83.00 112.00   1.00   13.50    --  115.00  61.00 150.00   29
 68  \w     82.00 176.00   1.00   13.50    --  115.00  61.00  30.00   94
 69  \w     84.00  96.00   1.00   13.50    --  115.00  54.00 112.88   12
;
_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      -0.0651592000
_diffrn_orient_matrix_UB_12      -0.0489658000
_diffrn_orient_matrix_UB_13      0.0671171000
_diffrn_orient_matrix_UB_21      0.0106360000
_diffrn_orient_matrix_UB_22      0.1325804000
_diffrn_orient_matrix_UB_23      0.0808970000
_diffrn_orient_matrix_UB_31      -0.1230573000
_diffrn_orient_matrix_UB_32      -0.0350581000
_diffrn_orient_matrix_UB_33      -0.0874981000
_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  0.0644
_diffrn_reflns_av_sigmaI/netI    0.0424
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            27959
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.242
_diffrn_reflns_theta_min         3.924
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.024
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.730
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.412
_exptl_crystal_description       irregular
_exptl_crystal_F_000             778
_exptl_crystal_size_max          0.174
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.053
_refine_diff_density_max         0.573
_refine_diff_density_min         -0.393
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         10019
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0792
_refine_ls_R_factor_gt           0.0590
_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^)+(0.1183P)^2^+0.0513P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1638
_refine_ls_wR_factor_ref         0.1768
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7365
_reflns_number_total             10019
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 2.6745\% 
around [-0.44 0.52 0.74] (reciprocal) or [0.07 0.68 0.73] (direct)
;
_cod_data_source_file            d2dt00583b2.cif
_cod_data_source_block           compound_2_Bipy
_cod_original_cell_volume        1755.33(16)
_cod_database_code               7710044
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C48H66F10N6O12S4Si6
_diffrn_oxdiff_digest_frames
;
011194f140eafd0171889f1edab3dcef0d000288ac0
;
_diffrn_oxdiff_digest_hkl
;
01b04f589c3e2bd21d5a1958e11f19f7f962f2
;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.627(3)
 0.373(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N3-C21 \\sim N4-C25
 with sigma of 0.02
 C22-C21 \\sim C26-C25
 with sigma of 0.02
4. Others
 Sof(S2B)=Sof(F4B)=Sof(O4B)=Sof(C24B)=1-FVAR(1)
 Sof(S2)=Sof(F4)=Sof(O4)=Sof(C24)=FVAR(1)
 Fixed Sof: N4(0.5) C25(0.5) C26(0.5) H26A(0.5) H26B(0.5) H26C(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C7(H7A,H7B), C8(H8A,H8B)
5.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C20(H20)
5.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C5(H5A,H5B,H5C),
 C6(H6A,H6B,H6C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              37801
_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 4.882
_oxdiff_exptl_absorpt_empirical_full_min 0.434
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2