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_1549317
_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_absolute_configuration rm
_chemical_formula_moiety         'C32 H12 B F24, C14 H26 Li O9'
_chemical_formula_sum            'C46 H38 B F24 Li O9'
_chemical_formula_weight         1208.51
_chemical_name_systematic
'(2,5,8,10,13,16,17,20,23-nonaoxabicyclo[7.7.7]tricosane)-lithium 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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-14
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-02-14 deposited with the CCDC.
2018-04-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8768(3)
_cell_length_b                   17.6754(4)
_cell_length_c                   22.1097(5)
_cell_measurement_temperature    293(2)
_cell_volume                     5032.2(2)
_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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.945
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            74838
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.550
_diffrn_reflns_theta_min         2.795
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.166
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6847
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker-2016/2) was used for absorption correction'
_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    1.595
_exptl_crystal_description       block
_exptl_crystal_F_000             2440
_exptl_crystal_preparation       'Chloroform solution'
_exptl_crystal_recrystallization_method
'Solvent layering of hexane over chloroform solution'
_exptl_crystal_size_max          0.172
_exptl_crystal_size_mid          0.167
_exptl_crystal_size_min          0.117
_refine_diff_density_max         0.465
_refine_diff_density_min         -0.397
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 4024 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.22(13)
_refine_ls_extinction_coef       0.0008(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     815
_refine_ls_number_reflns         12892
_refine_ls_number_restraints     252
_refine_ls_restrained_S_all      1.118
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0343P)^2^+2.0404P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0850
_refine_ls_wR_factor_ref         0.0929
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.879
_reflns_number_gt                10655
_reflns_number_total             12892
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01750f2.cif
_cod_data_source_block           hlo18001
_cod_depositor_comments
'Adding full bibliography for 1549313--1549320.cif.'
_cod_database_code               1549317
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F73-F72 \\sim F72-F71 \\sim F68-F70
 with sigma of 0.04
 C39-F73 \\sim C39-F72 \\sim C39-F69 \\sim C39-F68 \\sim C39-F70 \\sim C39-F71
\\sim C39-C22
 with sigma of 0.02
 F63-F65 \\sim F63-F66 \\sim F65-F66 \\sim F74-F75 \\sim F74-F76 \\sim F75-F76
 with sigma of 0.04
 C41-F63 \\sim C41-F65 \\sim C41-F66 \\sim C41-C21 \\sim C41-F74 \\sim C41-F75
\\sim C41-F76
 with sigma of 0.02
 C38-F55A \\sim C38-F67 \\sim C38-F64 \\sim C38-F55 \\sim C38-F64A \\sim
C38-F67A \\sim C38-C24
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C22, C39, F68, F69, F70
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22, C39, F71, F73, F72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C41, F63, F66, F65
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C21, C41, F76, F75, F74
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24, C38, F55, F67, F64
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24, C38, F64A, F55A, F67A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F71)=Sof(F72)=Sof(F73)=1-FVAR(1)
 Sof(F68)=Sof(F69)=Sof(F70)=FVAR(1)
 Sof(F74)=Sof(F75)=Sof(F76)=1-FVAR(2)
 Sof(F63)=Sof(F65)=Sof(F66)=FVAR(2)
 Sof(F67A)=Sof(F64A)=Sof(F55A)=1-FVAR(3)
 Sof(F55)=Sof(F64)=Sof(F67)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33)
5.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C32(H32A,H32B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,
 H36B), C37(H37A,H37B), C40(H40A,H40B), C42(H42A,H42B), C43(H43A,H43B),
 C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C8(H8), C10(H10), C11(H11), C12(H12), C14(H14), C15(H15),
 C16(H16), C17(H17), C23(H23), C28(H28)
;
_olex2_exptl_crystal_mounting_method 'by glowing'
_olex2_submission_special_instructions 'No special instructions were received'