Self-assembled orthoester cryptands: orthoester scope, post-functionalization, kinetic locking and tunable degradation kinetics.
Löw, Henrik; Mena-Osteritz, Elena; von Delius, Max; Chemical science 9 (2018) 4785–4793; doi:10.1039/c8sc01750f

data_1549316
_publ_section_title
;
 Self-assembled orthoester cryptands: orthoester scope,
 post-functionalization, kinetic locking and tunable degradation kinetics.
;
_journal_issue                   21
_journal_name_full               'Chemical science'
_journal_page_first              4785
_journal_page_last               4793
_journal_paper_doi               10.1039/c8sc01750f
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C24 H42 Na O9 Si2, C32 H12 B F24, 3(C3 H7)'
_chemical_formula_sum            'C65 H75 B F24 Na O9 Si2'
_chemical_formula_weight         1546.23
_chemical_name_systematic
'1,9-bis((trimethylsilyl)ethynyl)-2,5,8,10,13,16,17,20,23-nonaoxabicyclo[7.7.7]tricosane sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-03-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-03-27 deposited with the CCDC.
2018-04-27 downloaded from the CCDC.
;
_cell_angle_alpha                101.4174(19)
_cell_angle_beta                 103.600(2)
_cell_angle_gamma                101.486(2)
_cell_formula_units_Z            2
_cell_length_a                   13.9002(3)
_cell_length_b                   14.0497(3)
_cell_length_c                   21.1609(5)
_cell_measurement_reflns_used    15291
_cell_measurement_temperature    150.00(14)
_cell_measurement_theta_max      26.6730
_cell_measurement_theta_min      3.0890
_cell_volume                     3804.07(16)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(14)
_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 0.876
_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    -48.00  71.00   1.00   64.00    --   -9.42  19.00   0.00  119
  2  \w    -19.00  23.00   1.00   64.00    --   -9.42 -99.00 -60.00   42
  3  \w     -7.00  31.00   1.00   64.00    --   -9.42 -99.00  90.00   38
  4  \w     -9.00  17.00   1.00   64.00    --   -9.42 -57.00  30.00   26
  5  \w    -83.00  17.00   1.00   64.00    --   -9.42 -57.00   0.00  100
  6  \w     -8.00  19.00   1.00   64.00    --   -9.42 -99.00   0.00   27
  7  \w    -11.00  14.00   1.00   64.00    --   -9.42 -99.00 120.00   25
  8  \w     -9.00  28.00   1.00   64.00    --   -9.42 -99.00  30.00   37
  9  \w    -38.00 -11.00   1.00   64.00    --   11.14 -38.00  30.00   27
 10  \w    -20.00  48.00   1.00   64.00    --   11.14 -99.00 -90.00   68
 11  \w     73.00  98.00   1.00   64.00    --   11.14-178.00-180.00   25
 12  \w     49.00  74.00   1.00   64.00    --   11.14-178.00 150.00   25
;
_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      0.0164887000
_diffrn_orient_matrix_UB_12      -0.0345734000
_diffrn_orient_matrix_UB_13      -0.0216002000
_diffrn_orient_matrix_UB_21      -0.0276254000
_diffrn_orient_matrix_UB_22      0.0131639000
_diffrn_orient_matrix_UB_23      -0.0282492000
_diffrn_orient_matrix_UB_31      0.0437897000
_diffrn_orient_matrix_UB_32      0.0383803000
_diffrn_orient_matrix_UB_33      0.0029684000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0526
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.876
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            58033
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.876
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.460
_diffrn_reflns_theta_min         2.822
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.161
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87440
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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    1.350
_exptl_crystal_description       block
_exptl_crystal_F_000             1594
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.157
_exptl_crystal_size_min          0.122
_refine_diff_density_max         0.372
_refine_diff_density_min         -0.360
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1095
_refine_ls_number_reflns         18507
_refine_ls_number_restraints     872
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.1137
_refine_ls_R_factor_gt           0.0704
_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^)+(0.0552P)^2^+4.9330P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1618
_refine_ls_wR_factor_ref         0.1836
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11841
_reflns_number_total             18507
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01750f2.cif
_cod_data_source_block           hlo18020
_cod_depositor_comments
'Adding full bibliography for 1549313--1549320.cif.'
_cod_original_cell_volume        3804.08(16)
_cod_database_code               1549316
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C56H54BF24NaO9Si
_reflns_odcompleteness_completeness 99.87
_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
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C56-F1A \\sim C56-F4 \\sim C56-F1 \\sim C56-F0AA \\sim C56-F4A \\sim C56-F2A
\\sim C56-C27
 with sigma of 0.02
 F83A-F79A \\sim F79A-F69A \\sim F69-F83
 with sigma of 0.04
 C50-F83A \\sim C50-F79A \\sim C50-F79 \\sim C50-F69 \\sim C50-F83 \\sim
C50-F69A \\sim C50-C16
 with sigma of 0.02
 F75A-F61A \\sim F81A-F61A \\sim F75-F61 \\sim F81-F61
 with sigma of 0.04
 C55-F75A \\sim C55-F81A \\sim C55-F61A \\sim C55-F75 \\sim C55-F81 \\sim
C55-F61 \\sim C55-C45
 with sigma of 0.02
 F50-F57 \\sim F50-F66 \\sim F57-F66 \\sim F50A-F57A \\sim F50A-F66A \\sim
F57A-F66A
 with sigma of 0.04
 C54-F50 \\sim C54-F57 \\sim C54-C40 \\sim C54-F66 \\sim C54-F50A \\sim
C54-F57A \\sim C54-F66A
 with sigma of 0.02
 F66A-F57A \\sim F66A-F50A \\sim F50-F66 \\sim F50-F57 \\sim F57A-F50A \\sim
F66-F57
 with sigma of 0.04
 C54-F66A \\sim C54-F50 \\sim C54-F57A \\sim C54-F66 \\sim C54-F57 \\sim
C54-F50A \\sim C54-C40
 with sigma of 0.02
 C51-F68A \\sim C51-F80 \\sim C51-F68 \\sim C51-F67 \\sim C51-F67A \\sim
C51-C29 \\sim C51-F80A
 with sigma of 0.02
3. Rigid bond restraints
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17,
 C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33,
  C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, C47, C48,
 C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64,
  C65, C66, C67, C68
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57
\\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C27, C56, F4, F1, F0AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27, C56, F4A, F2A, F1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C50, F79, F69, F83
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C50, F69A, F83A, F79A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, C55, F61, F81, F75
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, C55, F81A, F61A, F75A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, C54, F66, F50, F57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, C54, F50A, F57A, F66A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C51, F68, F80, F67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C51, F68A, F67A, F80A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F4A)=Sof(F2A)=Sof(F1A)=1-FVAR(1)
 Sof(F1)=Sof(F0AA)=Sof(F4)=FVAR(1)
 Sof(F79A)=Sof(F83A)=Sof(F69A)=1-FVAR(2)
 Sof(F69)=Sof(F79)=Sof(F83)=FVAR(2)
 Sof(F81A)=Sof(F75A)=Sof(F61A)=1-FVAR(3)
 Sof(F61)=Sof(F75)=Sof(F81)=FVAR(3)
 Sof(F50A)=Sof(F57A)=Sof(F66A)=1-FVAR(4)
 Sof(F50)=Sof(F57)=Sof(F66)=FVAR(4)
 Sof(F80A)=Sof(F67A)=Sof(F68A)=1-FVAR(5)
 Sof(F67)=Sof(F68)=Sof(F80)=FVAR(5)
 Fixed Sof: H60D(0.5) H60E(0.5) H60F(0.5) H60A(0.5) H60B(0.5) H60C(0.5)
 C61(0.5) H61A(0.5) H61B(0.5) C62(0.5) H62A(0.5) H62B(0.5) C63(0.5) H63A(0.5)
 H63B(0.5) H64D(0.5) H64E(0.5) H64F(0.5) H64A(0.5) H64B(0.5) H64C(0.5) C65(0.5)
 H65A(0.5) H65B(0.5) C66(0.5) H66A(0.5) H66B(0.5) H67C(0.5) H67D(0.5) H67A(0.5)
 H67B(0.5) C68(0.5) H68A(0.5) H68B(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C18(H18A,H18B), C22(H22A,H22B), C25(H25A,H25B), C28(H28A,
 H28B), C31(H31A,H31B), C32(H32A,H32B), C36(H36A,H36B), C37(H37A,H37B),
 C38(H38A,H38B), C39(H39A,H39B), C43(H43A,H43B), C57(H57A,H57B), C58(H58A,H58B),
  C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C65(H65A,H65B), C66(H66A,
 H66B), C67(H67C,H67D), C67(H67A,H67B), C68(H68A,H68B)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C9(H9), C14(H14), C15(H15), C19(H19), C24(H24), C26(H26),
 C30(H30), C33(H33), C41(H41), C44(H44)
7.c Idealised Me refined as rotating group:
 C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C59(H59A,H59B,H59C), C60(H60D,
 H60E,H60F), C60(H60A,H60B,H60C), C64(H64D,H64E,H64F), C64(H64A,H64B,H64C)
;
_olex2_date_sample_data_collection 2018-03-06
_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 1.275
_oxdiff_exptl_absorpt_empirical_full_min 0.771