Competitive aminal formation during the synthesis of a highly soluble, isopropyl-decorated imine porous organic cage.
Kearsey, Rachel J.; Tarzia, Andrew; Little, Marc A.; Brand, Michael C.; Clowes, Rob; Jelfs, Kim E.; Cooper, Andrew I.; Greenaway, Rebecca L.; Chemical communications (Cambridge, England) 59 (2023) 3731–3734; doi:10.1039/d3cc00072a

data_7131321
_publ_section_title
;
 Competitive aminal formation during the synthesis of a highly soluble,
 isopropyl-decorated imine porous organic cage.
;
_journal_issue                   25
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3731
_journal_page_last               3734
_journal_paper_doi               10.1039/d3cc00072a
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety
'9(C H Cl3),10.5(C H4 O),2(C84 H120 N12),(H2 O)'
_chemical_formula_sum            'C187.5 H293 Cl27 N24 O11.5'
_chemical_formula_weight         4024.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_block_doi                 10.5517/ccdc.csd.cc2dzyfs
_audit_creation_date             2018-02-20
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.02.02 svn.r3481 for OlexSys, GUI svn.r5470)
;
_audit_update_record
;
2023-01-04 deposited with the CCDC.	2023-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.336(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.0941(13)
_cell_length_b                   45.047(4)
_cell_length_c                   16.4682(15)
_cell_measurement_reflns_used    9016
_cell_measurement_temperature    100
_cell_measurement_theta_max      23.659
_cell_measurement_theta_min      2.252
_cell_volume                     11514.2(17)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0589
_diffrn_reflns_av_unetI/netI     0.0721
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       50
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            84088
_diffrn_reflns_point_group_measured_fraction_full 0.832
_diffrn_reflns_point_group_measured_fraction_max 0.832
_diffrn_reflns_theta_full        23.256
_diffrn_reflns_theta_max         23.256
_diffrn_reflns_theta_min         1.359
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.373
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.5163
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. 
wR2(int) was 0.1625 before and 0.0780 after correction. The 
Ratio of minimum to maximum transmission is 0.6929. The \l/2 
correction factor is 0.00150.'
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_description       plate
_exptl_crystal_F_000             4274
_exptl_crystal_size_max          0.305
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.421
_refine_diff_density_min         -0.353
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 5409 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.21(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.500
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2135
_refine_ls_number_reflns         27498
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.521
_refine_ls_R_factor_all          0.1259
_refine_ls_R_factor_gt           0.0999
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2502
_refine_ls_wR_factor_ref         0.2647
_reflns_Friedel_coverage         0.640
_reflns_Friedel_fraction_full    0.659
_reflns_Friedel_fraction_max     0.659
_reflns_number_gt                18041
_reflns_number_total             27498
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc00072a2.cif
_cod_data_source_block           CC21_CHCl3_MeOH_100K_publ
_cod_depositor_comments
'Adding full bibliography for 7131321--7131322.cif.'
_cod_original_formula_sum        'C187.50 H293 Cl27 N24 O11.50'
_cod_database_code               7131321
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.895
_olex2_refinement_description
;
SQUEEZE was used during the final refinement cycles. Accordingly, the table
below was used to tentatively determine the amount of solvent molecules that
should be added to the unit cell atom count: 

Void  X(av) Y(av) Z(av) Volume Ang^3 El-Count (e-) Vol/Electron Vol/Atom        
1  0.075 0.351 0.825 761   236 (4x CHCl3 + 4x MeOH) 3.2 26        
2 -0.076 0.851 0.174 760   236 (4x CHCl3 + 4x MeOH) 3.2 26        
3  0.091 0.520-0.018 12   1  17.9      143        
4  0.122 0.596 0.362 21   3    7.6       61        
5  0.339 0.669 1.098 230 64 (CHCl3 + MeOH)3.6       29        
6  0.287 0.094 0.845 80   27 (MeOH)        2.9       24        
7  0.661 0.169 0.902 231   64 (CHCl3 + MeOH)3.6       29        
8  0.713 0.594 0.155 80   27 (MeOH)        2.9       24        
9  0.878 0.096 0.638 21   3 7.6       61        
0  0.909 0.020 0.018 12   1 17.6      141
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H17B,H17A,H172} of C172
 At 1.5 times of:
  All O(H) groups, {H39A,H39B,H39C} of C39, {H40A,H40B,H40C} of C40, {H43A,
  H43B,H43C} of C43, {H44A,H44B,H44C} of C44, {H46A,H46B,H46C} of C46, {H47A,
  H47B,H47C} of C47, {H50A,H50B,H50C} of C50, {H52A,H52B,H52C} of C52, {H55A,
  H55B,H55C} of C55, {H56A,H56B,H56C} of C56, {H59A,H59B,H59C} of C59, {H60A,
  H60B,H60C} of C60, {H63A,H63B,H63C} of C63, {H68A,H68B,H68C} of C68, {H66A,
  H66B,H66C} of C66, {H65A,H65B,H65C} of C65, {H12G,H12H,H12I} of C126, {H16A,
  H16B,H16C} of C160, {H15M,H15N,H15O} of C158, {H15J,H15K,H15L} of C157, {H15G,
  H15H,H15I} of C155, {H15D,H15E,H15F} of C152, {H15A,H15B,H15C} of C150, {H14M,
  H14N,H14O} of C149, {H14J,H14K,H14L} of C147, {H14G,H14H,H14I} of C144, {H14D,
  H14E,H14F} of C142, {H14A,H14B,H14C} of C141, {H13M,H13N,H13O} of C139, {H13J,
  H13K,H13L} of C136, {H13G,H13H,H13I} of C134, {H13D,H13E,H13F} of C133, {H13A,
  H13B,H13C} of C131, {H12J,H12K,H12L} of C128, {H84A,H84B,H84C} of C84, {H82A,
  H82B,H82C} of C82, {H81A,H81B,H81C} of C81, {H79A,H79B,H79C} of C79, {H76A,
  H76B,H76C} of C76, {H74A,H74B,H74C} of C74, {H73A,H73B,H73C} of C73, {H71A,
  H71B,H71C} of C71, {H12D,H12E,H12F} of C124, {H12A,H12B,H12C} of C122, {H17R,
  H17S,H17T} of C178, {H17C,H17D,H17E} of C177, {H17I,H17J,H17K} of C176, {H17F,
  H17G,H17H} of C175, {H17L,H17M,H17N} of C174, {H16M,H16N,H16O} of C168, {H16J,
  H16K,H16L} of C166, {H16G,H16H,H16I} of C165, {H16D,H16E,H16F} of C163, {H17O,
  H17P,H17Q} of C179, {H18A,H18B,H18C} of C182
2. Shared sites
{Cl18, C181}
3. Restrained distances
 Cl3-C170 = Cl3-C169 = Cl2-C170 = Cl2-C169 = Cl4-C170 = Cl1-C169
 1.74 with sigma of 0.01
 Cl15-C173 = Cl13-C173 = Cl14-C173
 1.74 with sigma of 0.01
 Cl5-C171 = Cl6-C171 = Cl7-C171
 1.74 with sigma of 0.01
 Cl19-C180 = Cl18-C180 = Cl17-C180 = Cl20-C180 = Cl16-C180
 1.74 with sigma of 0.01
 C181-Cl20
 1.74 with sigma of 0.01
 Cl21-C181 = Cl19-C181
 1.74 with sigma of 0.01
 O7-C178 = O5-C182 = O2-C175 = O1-C177 = O3-C176 = O4-C174 = O6-C179
 1.43 with sigma of 0.01
 N1-C26
 1.27 with sigma of 0.01
 N9-C35
 1.27 with sigma of 0.01
 C23-C22 = C23-C24 = C23-C27
 1.49 with sigma of 0.01
 C18-C14
 1.49 with sigma of 0.01
 Cl10-C172 = Cl12-C172 = Cl11-C172 = Cl8-C172
 1.74 with sigma of 0.01
 Cl13-Cl15
 2.83 with sigma of 0.02
 Cl13-Cl14
 2.83 with sigma of 0.02
 Cl15-Cl14
 2.83 with sigma of 0.02
 Cl11-Cl9
 2.83 with sigma of 0.02
 Cl11-Cl10
 2.83 with sigma of 0.02
 Cl20-Cl21 \\sim Cl21-Cl19 \\sim Cl19-Cl20
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(O9) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Cl18) = Uanis(C181)
5. Rigid body (RIGU) restrains
 Cl13, Cl14, Cl15, C173
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1, Cl2, Cl3, Cl4, C169, C170
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl5, Cl6, Cl7, C171
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C176, O3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C175
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6, C179
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl16, C180, Cl17, Cl18, Cl19, C181, Cl20, Cl21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, C182
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C177, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Cl1(0.25) Cl4(0.75) Cl5(0.75) Cl6(0.75) Cl7(0.75) Cl8(0.33333)
 Cl11(0.33333) Cl12(0.33333) Cl13(0.5) Cl14(0.5) Cl15(0.5) Cl16(0.5) Cl17(0.5)
 Cl18(0.5) Cl19(0.25) Cl20(0.25) Cl21(0.25) O1(0.5) H1(0.5) O2(0.5) H2A(0.5)
 O4(0.75) H4A(0.75) O5(0.5) H5(0.5) O6(0.75) H6A(0.75) O7(0.5) H7A(0.5)
 C169(0.25) H169(0.25) C170(0.75) H170(0.75) C171(0.75) H171(0.75)
 H17B(0.33333) H17A(0.33333) H172(0.33333) C173(0.5) H173(0.5) C174(0.75)
 H17L(0.75) H17M(0.75) H17N(0.75) C175(0.5) H17F(0.5) H17G(0.5) H17H(0.5)
 C177(0.5) H17C(0.5) H17D(0.5) H17E(0.5) C178(0.5) H17R(0.5) H17S(0.5)
 H17T(0.5) C179(0.75) H17O(0.75) H17P(0.75) H17Q(0.75) C180(0.5) H180(0.5)
 C181(0.25) H181(0.25) C182(0.5) H18A(0.5) H18B(0.5) H18C(0.5) O8(0.5) O9(0.25)
 O10(0.25)
7.a Ternary CH refined with riding coordinates:
 C37(H37), C38(H38), C41(H41), C42(H42), C45(H45), C48(H48), C49(H49),
 C51(H51), C53(H53), C54(H54), C57(H57), C58(H58), C61(H61), C62(H62), C64(H64),
  C67(H67), C69(H69), C70(H70), C72(H72), C75(H75), C77(H77), C78(H78),
 C80(H80), C83(H83), C121(H121), C123(H123), C125(H125), C127(H127), C129(H129),
  C130(H130), C132(H132), C135(H135), C137(H137), C138(H138), C140(H140),
 C143(H143), C145(H145), C146(H146), C148(H148), C151(H151), C153(H153),
 C154(H154), C156(H156), C159(H159), C161(H161), C162(H162), C164(H164),
 C167(H167), C169(H169), C170(H170), C171(H171), C172(H17B), C172(H17A),
 C172(H172), C173(H173), C180(H180), C181(H181)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C13(H13), C15(H15),
 C16(H16), C17(H17), C18(H18), C22(H22), C20(H20), C24(H24), C25(H25), C26(H26),
  C27(H27), C29(H29), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36),
 C86(H86), C88(H88), C90(H90), C91(H91), C92(H92), C93(H93), C95(H95), C97(H97),
  C99(H99), C100(H100), C101(H101), C102(H102), C104(H104), C106(H106),
 C108(H108), C109(H109), C110(H110), C111(H111), C113(H113), C115(H115),
 C117(H117), C118(H118), C119(H119), C120(H120)
7.c Fitted hexagon refined as free rotating group:
 C23(C22,C21,C20,C19,C24)
7.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C50(H50A,H50B,H50C), C52(H52A,
 H52B,H52C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C59(H59A,H59B,H59C),
 C60(H60A,H60B,H60C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C), C66(H66A,H66B,
 H66C), C68(H68A,H68B,H68C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C74(H74A,
 H74B,H74C), C76(H76A,H76B,H76C), C79(H79A,H79B,H79C), C81(H81A,H81B,H81C),
 C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C122(H12A,H12B,H12C), C124(H12D,H12E,
 H12F), C126(H12G,H12H,H12I), C128(H12J,H12K,H12L), C131(H13A,H13B,H13C),
 C133(H13D,H13E,H13F), C134(H13G,H13H,H13I), C136(H13J,H13K,H13L), C139(H13M,
 H13N,H13O), C141(H14A,H14B,H14C), C142(H14D,H14E,H14F), C144(H14G,H14H,H14I),
 C147(H14J,H14K,H14L), C149(H14M,H14N,H14O), C150(H15A,H15B,H15C), C152(H15D,
 H15E,H15F), C155(H15G,H15H,H15I), C157(H15J,H15K,H15L), C158(H15M,H15N,H15O),
 C160(H16A,H16B,H16C), C163(H16D,H16E,H16F), C165(H16G,H16H,H16I), C166(H16J,
 H16K,H16L), C168(H16M,H16N,H16O), C174(H17L,H17M,H17N), C175(H17F,H17G,H17H),
 C176(H17I,H17J,H17K), C177(H17C,H17D,H17E), C178(H17R,H17S,H17T), C179(H17O,
 H17P,H17Q), C182(H18A,H18B,H18C)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2A), O3(H3), O4(H4A), O5(H5), O6(H6A), O7(H7A)
;
_olex2_submission_special_instructions 'No special instructions were received'