Self-templated synthesis of an orthoformate in,in-cryptand and its bridgehead inversion by dynamic covalent exchange
Löw, Henrik; Mena-Osteritz, Elena; von Delius, Max; Chemical Communications  (2019) –; doi:10.1039/C9CC05968G

data_7124117
_publ_section_title
;
 Self-templated synthesis of an orthoformate in,in-cryptand and its
 bridgehead inversion by dynamic covalent exchange
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC05968G
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H26 Na O9, C32 H12 B F24'
_chemical_formula_sum            'C46 H38 B F24 Na O9'
_chemical_formula_weight         1224.56
_chemical_name_systematic
'(2,5,8,10,13,16,17,20,23-nonaoxabicyclo[7.7.7]tricosane)-natrium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-10-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-10-30 deposited with the CCDC.    2019-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1390(3)
_cell_length_b                   17.7561(3)
_cell_length_c                   21.7663(5)
_cell_measurement_reflns_used    22147
_cell_measurement_temperature    149.95(10)
_cell_measurement_theta_max      27.9880
_cell_measurement_theta_min      2.9530
_cell_volume                     5078.02(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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      149.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3385
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.923
_diffrn_measurement_details
;
  1 omega  -16.00   30.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.4167  -99.0000   90.0000 46

  2 omega  -17.00   30.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.4167  -99.0000 -150.0000 47

  3 omega   -2.00   25.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.4167  -99.0000  -30.0000 27

  4 omega  -77.00  -23.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.4167  -38.0000  150.0000 54

  5 omega  -83.00    0.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.4167  -38.0000 -150.0000 83

  6 omega  -24.00   59.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       -9.4167   38.0000    0.0000 83

  7 omega   -7.00   19.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       11.1355  -99.0000    0.0000 26

  8 omega   -2.00   27.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       11.1355  -57.0000   90.0000 29

  9 omega  -50.00  -23.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       11.1355  -57.0000   90.0000 27

 10 omega   42.00   92.00   1.0000   64.0000
omega____ theta____ kappa____ phi______ frames
    -       11.1355  178.0000 -180.0000 50
;
_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      0.0297566000
_diffrn_orient_matrix_UB_12      0.0044425000
_diffrn_orient_matrix_UB_13      -0.0269589000
_diffrn_orient_matrix_UB_21      0.0407401000
_diffrn_orient_matrix_UB_22      -0.0194279000
_diffrn_orient_matrix_UB_23      0.0142813000
_diffrn_orient_matrix_UB_31      -0.0191229000
_diffrn_orient_matrix_UB_32      -0.0346259000
_diffrn_orient_matrix_UB_33      -0.0114969000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0419
_diffrn_reflns_av_unetI/netI     0.0356
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.923
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            67161
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.901
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.550
_diffrn_reflns_theta_min         2.769
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.174
_exptl_absorpt_correction_T_max  0.986
_exptl_absorpt_correction_T_min  0.972
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.602
_exptl_crystal_F_000             2472
_exptl_crystal_preparation       'Chloroform solution'
_exptl_crystal_recrystallization_method
'solvent layering of hexane over choloform solution'
_exptl_crystal_size_max          0.2282
_exptl_crystal_size_mid          0.1705
_exptl_crystal_size_min          0.0955
_refine_diff_density_max         0.644
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 3761 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.08(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     860
_refine_ls_number_reflns         12798
_refine_ls_number_restraints     481
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0382P)^2^+2.4909P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0948
_refine_ls_wR_factor_ref         0.1049
_reflns_Friedel_coverage         0.784
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.873
_reflns_number_gt                10195
_reflns_number_total             12798
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc05968g2.cif
_cod_data_source_block           hlo18006
_cod_original_cell_volume        5078.00(19)
_cod_database_code               7124117
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C46 H38 B F24 Na O9'
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 F22A-F24A \\sim F24A-F23A \\sim F24-F22 \\sim F23-F22
 with sigma of 0.04
 C33-F22A \\sim C33-F24A \\sim C33-F24 \\sim C33-F23 \\sim C33-F22 \\sim
C33-C22 \\sim C33-F23A
 with sigma of 0.02
 C27-F19A \\sim C27-F21A \\sim C27-F17A \\sim C27-F17 \\sim C27-F19 \\sim
C27-F21 \\sim C27-C18
 with sigma of 0.02
 F10-F16 \\sim F10-F20 \\sim F16-F20 \\sim F20A-F16A \\sim F20A-F10A \\sim
F16A-F10A
 with sigma of 0.04
 C31-F10 \\sim C31-F16 \\sim C31-F20 \\sim C31-C14 \\sim C31-F20A \\sim
C31-F16A \\sim C31-F10A
 with sigma of 0.02
 F6-F11 \\sim F6-F12 \\sim F11-F12 \\sim F12A-F11A \\sim F12A-F6A
 with sigma of 0.04
 C28-F6 \\sim C28-F11 \\sim C28-F12 \\sim C28-C21 \\sim C28-F12A \\sim C28-F11A
\\sim C28-F6A
 with sigma of 0.02
3. Rigid bond restraints
 F1, F2, F3, F4, F5, F6, F7, F8, F9, F10, F11, F12, F13, F14, F15, F16, F17,
 F18, F19, F20, F21, F22, F23, F24, F24A, F23A, F22A, F19A, F17A, F21A, F20A,
 F16A, F10A, F12A, F11A, F6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F21 \\sim F21A \\sim F17 \\sim F17A \\sim F19 \\sim F19A \\sim F23 \\sim F23A
\\sim F22 \\sim F22A \\sim F24 \\sim F24A \\sim F18 \\sim F20A \\sim F20 \\sim
F16 \\sim F16A \\sim F10A \\sim F10 \\sim F14 \\sim F1 \\sim F2 \\sim F3 \\sim
F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim F9 \\sim F11 \\sim F12 \\sim F13
\\sim F15 \\sim F12A \\sim F11A \\sim F6A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C22, C33, F24, F23, F22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22, C33, F24A, F23A, F22A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18, C27, F17, F19, F21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18, C27, F21A, F17A, F19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, C31, F20, F16, F10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C14, C31, F20A, F16A, F10A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C28, F12, F11, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C28, F12A, F6A, F11A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F24A)=Sof(F23A)=Sof(F22A)=1-FVAR(1)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(1)
 Sof(F19A)=Sof(F17A)=Sof(F21A)=1-FVAR(2)
 Sof(F17)=Sof(F19)=Sof(F21)=FVAR(2)
 Sof(F20A)=Sof(F16A)=Sof(F10A)=1-FVAR(3)
 Sof(F10)=Sof(F16)=Sof(F20)=FVAR(3)
 Sof(H42C)=Sof(H42D)=Sof(O4A)=1-FVAR(4)
 Sof(H42A)=Sof(H42B)=Sof(O4)=FVAR(4)
 Sof(F12A)=Sof(F11A)=Sof(F6A)=1-FVAR(5)
 Sof(F6)=Sof(F11)=Sof(F12)=FVAR(5)
7.a Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,
 H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C42(H42C,H42D),
 C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B)
7.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13),
 C16(H16), C19(H19), C24(H24), C26(H26)
;
_ins_header
;
TITL HLO18006 in P2(1)2(1)2(1) 
REM P2(1)2(1)2(1) (#19 in standard setting)
CELL 0.71073  13.138974  17.756049  21.766312  90.0000  90.0000  90.0000
ZERR    4.00   0.000322   0.000332   0.000484   0.0000   0.0000   0.0000
LATT -1
SYMM -x+1/2,-y, z+1/2 
SYMM -x, y+1/2,-z+1/2 
SYMM  x+1/2,-y+1/2,-z 
SFAC C H B O F Na
UNIT 184.00 152.00 4.00 36.00 96.00 4.00
TREF
HKLF 4
END
;
_olex2_date_sample_data_collection 2018-01-29
_olex2_exptl_crystal_mounting_method glowing
_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 1.170
_oxdiff_exptl_absorpt_empirical_full_min 0.813