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_1549318
_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
'2(C18 H26 Na O9), 2(C H Cl3), 2(C32 H12 B F24)'
_chemical_formula_sum            'C102 H78 B2 Cl6 F48 Na2 O18'
_chemical_formula_weight         2783.94
_chemical_name_systematic
'(1,9-diethynyl-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     iterative
_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                70.108(16)
_cell_angle_beta                 83.341(17)
_cell_angle_gamma                89.951(13)
_cell_formula_units_Z            2
_cell_length_a                   16.654(8)
_cell_length_b                   18.497(8)
_cell_length_c                   20.536(9)
_cell_measurement_reflns_used    9709
_cell_measurement_temperature    293.15
_cell_measurement_theta_max      23.25
_cell_measurement_theta_min      2.33
_cell_volume                     5903(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      293.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0556
_diffrn_reflns_av_unetI/netI     0.0391
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            122948
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        23.259
_diffrn_reflns_theta_max         23.259
_diffrn_reflns_theta_min         2.125
_diffrn_source                   'sealed tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.291
_exptl_absorpt_correction_T_max  0.7449
_exptl_absorpt_correction_T_min  0.6782
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0872 before and 0.0736 after correction.
The Ratio of minimum to maximum transmission is 0.9105.
The \l/2 correction factor is Not present.
;
_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    1.566
_exptl_crystal_description       rods
_exptl_crystal_F_000             2800
_exptl_crystal_preparation       'Chloroform solution'
_exptl_crystal_recrystallization_method
'Solvent layering of hexane over the chloroform solution'
_exptl_crystal_size_max          0.289
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.111
_refine_diff_density_max         0.669
_refine_diff_density_min         -0.584
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2075
_refine_ls_number_reflns         16871
_refine_ls_number_restraints     1118
_refine_ls_restrained_S_all      1.178
_refine_ls_R_factor_all          0.0783
_refine_ls_R_factor_gt           0.0632
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0378P)^2^+14.5804P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1442
_refine_ls_wR_factor_ref         0.1547
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13711
_reflns_number_total             16871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01750f2.cif
_cod_data_source_block           hl17065_0m_a
_cod_depositor_comments
'Adding full bibliography for 1549313--1549320.cif.'
_cod_database_code               1549318
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.921
_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
 O01F-O01I \\sim O01F-O010 \\sim O01I-O010 \\sim O0-O0AA \\sim O0-O01G \\sim
O0AA-O01G
 with sigma of 0.04
 C40-O01F \\sim C40-O01I \\sim C40-O010 \\sim C40-C84 \\sim C40-O0 \\sim
C40-O0AA \\sim C40-O01G
 with sigma of 0.02
 O01Q-O02N \\sim O01Q-O025 \\sim O02N-O025 \\sim O01R-O1 \\sim O01R-O02O \\sim
O1-O02O
 with sigma of 0.04
 C44-O01Q \\sim C44-O02N \\sim C44-O025 \\sim C44-C91 \\sim C44-O01R \\sim
C44-O1 \\sim C44-O02O
 with sigma of 0.02
 C95-C33 \\sim C95-F039 \\sim C95-F04W \\sim C95-F0
 with sigma of 0.02
 O01J-O01K \\sim O01J-O017 \\sim O01K-O017 \\sim O2-O01L \\sim O2-O1AA \\sim
O01L-O1AA
 with sigma of 0.04
 C94-O01J \\sim C94-O01K \\sim C94-C71 \\sim C94-O017 \\sim C94-O2 \\sim
C94-O01L \\sim C94-O1AA
 with sigma of 0.02
 O00W-O013 \\sim O00X-O4
 with sigma of 0.04
 C85-O00W \\sim C85-C55 \\sim C85-O013 \\sim C85-O014 \\sim C85-O00X \\sim
C85-O3 \\sim C85-O4
 with sigma of 0.02
 F03P-F04C \\sim F03P-F04K \\sim F04C-F04K \\sim F04L-F04D \\sim F04L-F03Q
\\sim F04D-F03Q
 with sigma of 0.04
 C98-F03P \\sim C98-F04C \\sim C98-F04K \\sim C98-C36 \\sim C98-F04L \\sim
C98-F04D \\sim C98-F03Q
 with sigma of 0.02
 Cl00-Cl1 \\sim Cl00-Cl5 \\sim Cl1-Cl5
 with sigma of 0.04
 C97-F015 \\sim C97-F031 \\sim C97-F02O \\sim C97-C74
 with sigma of 0.02
 F04W-F0 \\sim F04W-F2 \\sim F04X-F0A
 with sigma of 0.04
 C95-C33 \\sim C95-F039 \\sim C95-F04W \\sim C95-F0 \\sim C95-F04X \\sim
C95-F0A \\sim C95-F2
 with sigma of 0.02
 F4-F6 \\sim F4-F7 \\sim F6-F7 \\sim F7A-F4A \\sim F7A-F6A \\sim F4A-F6A
 with sigma of 0.04
 C92-C16 \\sim C92-F4 \\sim C92-F6 \\sim C92-F7 \\sim C92-F7A \\sim C92-F4A
\\sim C92-F6A
 with sigma of 0.02
 F0AA-F8 \\sim F0AA-F9 \\sim F8A-F0AB \\sim F8A-F9A \\sim F8-F9
 with sigma of 0.04
 C63-F0AA \\sim C63-F8A \\sim C63-F8 \\sim C63-F9 \\sim C63-F0AB \\sim C63-F9A
\\sim C63-C31
 with sigma of 0.02
 C106-Cl3A \\sim C106-Cl2A \\sim C106-Cl4A
 with sigma of 0.02
 C99-Cl2 \\sim C99-Cl3 \\sim C99-Cl4
 with sigma of 0.02
 F04J-F00Z \\sim F04J-F035 \\sim F00Z-F035
 with sigma of 0.04
 C86-F04J \\sim C86-F00Z \\sim C86-C26 \\sim C86-F035
 with sigma of 0.02
 F1AA-F2AA \\sim F1AA-F5 \\sim F2AA-F5 \\sim F5A-F1AB \\sim F5A-F2AB \\sim
F1AB-F2AB
 with sigma of 0.04
 C89-C20 \\sim C89-F1AA \\sim C89-F2AA \\sim C89-F5 \\sim C89-F5A \\sim
C89-F1AB \\sim C89-F2AB
 with sigma of 0.02
 Cl00-Cl1 \\sim Cl00-Cl5 \\sim Cl1-Cl5 \\sim Cl0A-Cl1A
 with sigma of 0.04
 C105-Cl00 \\sim C105-Cl1 \\sim C105-Cl5 \\sim C105-Cl0A \\sim C105-Cl1A
 with sigma of 0.02
 F10-F02P \\sim F10-F11
 with sigma of 0.04
 C97-F10 \\sim C97-F02P \\sim C97-F015 \\sim C97-F031 \\sim C97-F02O \\sim
C97-F11 \\sim C97-C74
 with sigma of 0.02
 F3AB-F4AB \\sim F4AB-F3A
 with sigma of 0.04
 C96-F3AB \\sim C96-F4AB \\sim C96-F3 \\sim C96-F3AA \\sim C96-F4AA \\sim
C96-C41 \\sim C96-F3A
 with sigma of 0.02
 C86-F1 \\sim C86-F04J \\sim C86-F5AA \\sim C86-F00Z \\sim C86-F035 \\sim
C86-C26 \\sim C86-F00{
 with sigma of 0.02
3. Rigid bond restraints
 Cl00, Cl1, Cl2, Cl3, Cl4, Cl5, Cl3A, Cl2A, Cl4A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Cl00 \\sim Cl1 \\sim Cl2 \\sim Cl3 \\sim Cl4 \\sim Cl5 \\sim Cl3A \\sim Cl2A
\\sim Cl4A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C91, C44, O01Q, O02N, O025
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O02O, C44, O01R, C91, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, O0, C84, O0AA, O01G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, O01I, O010, O01F, C84
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C95, F039
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C95, F04W, F0
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C85, O00W, O013, O014, C55, C94, O01K, O01J, O017, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C94, C71, O2, O01L, O1AA, C85, O00X, O3, O4, C55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C63, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C99, Cl2, Cl4, Cl3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C36, C98, F04K, F03P, F04C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C36, C98, F03Q, F04D, F04L
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C92, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C92
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C86, F04J, F00Z, F035
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1, Cl5, Cl00
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C89
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, C96
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33, C95, F04X, F2, F0A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C33, C95, F04W, F039, F0
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C92, F6, F4, F7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C92, F4A, F6A, F7A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, C63, F9, F0AA, F8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31, C63, F8A, F0AB, F9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C89, F5, F2AA, F1AA
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20, C89, F2AB, F1AB, F5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C105, Cl00, Cl1, Cl5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C105, Cl5A, Cl0A, Cl1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C86, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C86, F00Z, F035, F04J
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C74, C97, F015, F02O, F031
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C74, C97, F02P, F10, F11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, C96, F3AA, F4AA, F3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41, C96, F3AB, F4AB, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C86
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C86, F04J, F035, F00Z
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C86, F035, F00Z, F04J
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26, C86, F5AA, F00{, F1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H60C)=Sof(H60D)=Sof(H64C)=Sof(H64D)=Sof(H88C)=Sof(H88D)=Sof(O0)=Sof(O0AA)=
 Sof(O01G)=1-FVAR(1)
 Sof(O01F)=Sof(O01I)=Sof(H60A)=Sof(H60B)=Sof(H64A)=Sof(H64B)=Sof(O010)=
 Sof(H88A)=Sof(H88B)=FVAR(1)
 Sof(H69C)=Sof(H69D)=Sof(O01R)=Sof(O1)=Sof(H10M)=Sof(H10N)=1-FVAR(2)
 Sof(O01Q)=Sof(H69A)=Sof(H69B)=Sof(O025)=Sof(H10K)=Sof(H10L)=FVAR(2)
 Sof(H68C)=Sof(H68D)=Sof(O2)=Sof(O01L)=Sof(O1AA)=1-FVAR(3)
 Sof(O01J)=Sof(O01K)=Sof(H68A)=Sof(H68B)=Sof(O017)=FVAR(3)
 Sof(H57C)=Sof(H57D)=Sof(H66C)=Sof(H66D)=Sof(O00X)=Sof(O3)=Sof(O4)=1-FVAR(4)
 Sof(O00W)=Sof(H57A)=Sof(H57B)=Sof(H66A)=Sof(H66B)=Sof(O013)=Sof(O014)=FVAR(4)
 Sof(F04L)=Sof(F04D)=Sof(F03Q)=1-FVAR(5)
 Sof(F03P)=Sof(F04C)=Sof(F04K)=FVAR(5)
 Sof(F04X)=Sof(F0A)=Sof(F2)=1-FVAR(6)
 Sof(F039)=Sof(F04W)=Sof(F0)=FVAR(6)
 Sof(F7A)=Sof(F4A)=Sof(F6A)=1-FVAR(7)
 Sof(F4)=Sof(F6)=Sof(F7)=FVAR(7)
 Sof(F9A)=Sof(F0AB)=Sof(F8A)=1-FVAR(8)
 Sof(F0AA)=Sof(F8)=Sof(F9)=FVAR(8)
 Sof(C106)=Sof(H106)=Sof(Cl3A)=Sof(Cl2A)=Sof(Cl4A)=1-FVAR(9)
 Sof(Cl2)=Sof(Cl3)=Sof(Cl4)=Sof(C99)=Sof(H99)=FVAR(9)
 Sof(F5A)=Sof(F1AB)=Sof(F2AB)=1-FVAR(10)
 Sof(F1AA)=Sof(F2AA)=Sof(F5)=FVAR(10)
 Sof(F10)=Sof(F02P)=Sof(F11)=1-FVAR(11)
 Sof(F02O)=Sof(F015)=Sof(F031)=FVAR(11)
 Sof(F4AB)=Sof(F3A)=Sof(F3AB)=1-FVAR(12)
 Sof(F3AA)=Sof(F4AA)=Sof(F3)=FVAR(12)
 Sof(F5AA)=Sof(F00{)=Sof(F1)=1-FVAR(13)
 Sof(F04J)=Sof(F00Z)=Sof(F035)=FVAR(13)
 Fixed Sof: Cl00(0.5) Cl1(0.5) Cl5(0.5) O01C(0.75) O01D(0.75) O02N(0.75)
 H47A(0.75) H47B(0.75) H47C(0.25) H47D(0.25) H49A(0.75) H49B(0.75) H49C(0.25)
 H49D(0.25) H50A(0.75) H50B(0.75) H50C(0.25) H50D(0.25) H51A(0.75) H51B(0.75)
 H51C(0.25) H51D(0.25) H52A(0.75) H52B(0.75) H52C(0.25) H52D(0.25) H54A(0.75)
 H54B(0.75) H54C(0.25) H54D(0.25) H56A(0.75) H56B(0.75) H56C(0.25) H56D(0.25)
 C65(0.75) H65A(0.75) H65B(0.75) C67(0.75) H67A(0.75) H67B(0.75) C70(0.75)
 H70A(0.75) H70B(0.75) O016(0.75) O018(0.75) H87A(0.75) H87B(0.75) H87C(0.25)
 H87D(0.25) O02O(0.25) O2AA(0.25) C100(0.25) H10A(0.25) H10B(0.25) C101(0.25)
 H10C(0.25) H10D(0.25) O3AA(0.25) C102(0.25) H10E(0.25) H10F(0.25) O5AA(0.25)
 H10G(0.75) H10H(0.75) H10I(0.25) H10J(0.25) O6AA(0.25) C105(0.5) H105(0.5)
 Cl0A(0.5) Cl1A(0.5) Cl5A(0.5) C107(0.5) H107(0.5)
7.a Ternary CH refined with riding coordinates:
 C99(H99), C105(H105), C106(H106), C107(H107)
7.b Secondary CH2 refined with riding coordinates:
 C47(H47A,H47B), C47(H47C,H47D), C49(H49A,H49B), C49(H49C,H49D), C50(H50A,
 H50B), C50(H50C,H50D), C51(H51A,H51B), C51(H51C,H51D), C52(H52A,H52B),
 C52(H52C,H52D), C53(H53A,H53B), C54(H54A,H54B), C54(H54C,H54D), C56(H56A,H56B),
  C56(H56C,H56D), C57(H57A,H57B), C57(H57C,H57D), C59(H59A,H59B), C60(H60A,
 H60B), C60(H60C,H60D), C61(H61A,H61B), C62(H62A,H62B), C64(H64A,H64B),
 C64(H64C,H64D), C65(H65A,H65B), C66(H66A,H66B), C66(H66C,H66D), C67(H67A,H67B),
  C68(H68A,H68B), C68(H68C,H68D), C69(H69A,H69B), C69(H69C,H69D), C70(H70A,
 H70B), C87(H87A,H87B), C87(H87C,H87D), C88(H88A,H88B), C88(H88C,H88D),
 C100(H10A,H10B), C101(H10C,H10D), C102(H10E,H10F), C103(H10G,H10H), C103(H10I,
 H10J), C104(H10K,H10L), C104(H10M,H10N)
7.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C12(H12), C13(H13), C19(H19), C21(H21), C23(H23),
 C24(H24), C25(H25), C28(H28), C30(H30), C34(H34), C37(H37), C38(H38), C39(H39),
  C42(H42), C72(H72), C76(H76), C77(H77), C78(H78), C80(H80), C81(H81), C82(H82)
7.d :
 C1(H1), C2(H2), C3(H3), C4(H4)
;
_olex2_exptl_crystal_mounting_method 'by glowing'
_olex2_submission_special_instructions 'No special instructions were received'