Facile Synthetic Routes to Bridge-Functionalised Calix[4]arenes
Fong, Angela; Cambell, Cameron; Huynh, Silvia; McCormick McPherson, Laura J.; Teat, Simon; Bebbington, Magnus W. P.; Dalgarno, Scott; Chemical Communications  (2022) –; doi:10.1039/D1CC06889J

data_7129657
_publ_section_title
;
 Facile Synthetic Routes to Bridge-Functionalised Calix[4]arenes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06889J
_journal_year                    2022
_chemical_formula_moiety         '2(C68 H80 O12), 1.25(C8 H12 N4)'
_chemical_formula_sum            'C146 H175 N5 O24'
_chemical_formula_weight         2383.90
_space_group_crystal_system      tetragonal
_space_group_IT_number           100
_space_group_name_Hall           'P 4 -2ab'
_space_group_name_H-M_alt        'P 4 b m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2022-01-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-01-24 deposited with the CCDC.	2022-02-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   25.0238(7)
_cell_length_b                   25.0238(7)
_cell_length_c                   10.8155(6)
_cell_measurement_reflns_used    10082
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      26.7100
_cell_measurement_theta_min      3.4610
_cell_volume                     6772.6(5)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_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    -88.00  19.00   1.00   10.00    --   -9.43 -19.00-120.00  107
  2  \w    -18.00  30.00   1.00   10.00    --   -9.43 -99.00 150.00   48
  3  \w    -44.00  -7.00   1.00   10.00    --   -9.43 100.00 177.14   37
  4  \w      5.00  56.00   1.00   10.00    --   10.84-127.00 127.00   51
  5  \w    -14.00  13.00   1.00   10.00    --   10.84  57.00  90.00   27
  6  \w     -1.00  25.00   1.00   10.00    --   10.84-122.00  11.80   26
  7  \w     48.00  75.00   1.00   10.00    --   10.84  19.00-120.00   27
  8  \w    -38.00 -11.00   1.00   10.00    --   10.84 -77.00  90.00   27
  9  \w     12.00  37.00   1.00   10.00    --   10.84 -57.00  90.00   25
 10  \w    -62.00 -25.00   1.00   10.00    --   10.84 -77.00   0.00   37
;
_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      -0.0011987000
_diffrn_orient_matrix_UB_12      -0.0273592000
_diffrn_orient_matrix_UB_13      -0.0169601000
_diffrn_orient_matrix_UB_21      0.0020463000
_diffrn_orient_matrix_UB_22      0.0072151000
_diffrn_orient_matrix_UB_23      -0.0632291000
_diffrn_orient_matrix_UB_31      0.0282488000
_diffrn_orient_matrix_UB_32      -0.0016622000
_diffrn_orient_matrix_UB_33      0.0038552000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0831
_diffrn_reflns_av_unetI/netI     0.0440
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            73696
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         26.996
_diffrn_reflns_theta_min         2.935
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.519
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.169
_exptl_crystal_description       block
_exptl_crystal_F_000             2556
_exptl_crystal_size_max          0.383
_exptl_crystal_size_mid          0.295
_exptl_crystal_size_min          0.161
_refine_diff_density_max         0.217
_refine_diff_density_min         -0.219
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2423 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.1(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         7480
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.101
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0520
_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^)+(0.0328P)^2^+2.6835P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1006
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.860
_reflns_Friedel_fraction_full    0.966
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                6635
_reflns_number_total             7480
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06889j2.cif
_cod_data_source_block           2
_cod_database_code               7129657
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C68 H80 O12'
_chemical_oxdiff_usercomment     '@ 120 K AF148'
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Others
 Fixed Sof: C32(0.5) H32A(0.5) H32B(0.5) H32C(0.5) C33(0.5) H33A(0.5)
 H33B(0.5) H33C(0.5) C34(0.5) H34A(0.5) H34B(0.5) H34C(0.5) H35A(0.5) H35B(0.5)
 H35C(0.5) H36A(0.5) H36B(0.5) H36C(0.5) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5)
 C29(0.5) H29A(0.5) H29B(0.5) H29C(0.5) C30(0.5) H30A(0.5) H30B(0.5) H30C(0.5)
 H42A(0.25) H42B(0.25) H42C(0.25) H44A(0.5) H44B(0.5) H44C(0.5) N3(0.5)
 C46(0.5) H46A(0.5) H46B(0.5) H46C(0.5) C47(0.5)
2.a Everything fixed:
 H42A, H42B, H42C
2.b Ternary CH refined with riding coordinates:
 C7(H7), C22(H22)
2.c Me refined with riding coordinates:
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C)
2.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C14(H14), C15(H15), C19(H19), C24(H24), C38(H38), C39(H39)
2.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C17(H17A,H17B,H17C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C41(H41A,
 H41B,H41C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C44(H44A,H44B,H44C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              21697
_shelx_hkl_checksum              82263
_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 1.312
_oxdiff_exptl_absorpt_empirical_full_min 0.797