Rigidification of a Macrocyclic Tris-Catecholate Scaffold Leads to Electronic Localisation of its Mixed Valent Redox Product
Greatorex, Sam; Vincent, Kevin B.; Baldansuren, Amgalanbaatar; McInnes, Eric J. L.; Patmore, Nathan John; Sproules, Stephen; Halcrow, Malcolm; Chemical Communications  (2019) –; doi:10.1039/C8CC10122A

data_7122912
_publ_section_title
;
 Rigidification of a Macrocyclic Tris-Catecholate Scaffold Leads to
 Electronic Localisation of its Mixed Valent Redox Product
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C8CC10122A
_journal_year                    2019
_chemical_formula_moiety         'C26 H24 O6, C4 H8 O, 0.15(C H4 O)'
_chemical_formula_sum            'C30.15 H32.6 O7.15'
_chemical_formula_weight         509.36
_chemical_name_systematic
'2,3,6,7,10,11-Hexahydroxy-4b,8b,12b,12d-tetramethyltribenzo-triquinacene tetrahydrofuran (1/1) methanol (0.5/0.15) solvate'
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-12-18
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:54:37, GUI svn.r4466)
;
_audit_update_record
;
2018-12-18 deposited with the CCDC.
2019-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                67.602(12)
_cell_angle_beta                 67.891(11)
_cell_angle_gamma                62.042(13)
_cell_formula_units_Z            2
_cell_length_a                   11.1115(13)
_cell_length_b                   11.3585(16)
_cell_length_c                   12.7308(15)
_cell_measurement_reflns_used    2394
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.16
_cell_measurement_theta_min      3.86
_cell_volume                     1273.1(3)
_computing_cell_refinement       'CrysAlisPro, Agilent Technologies'
_computing_data_collection       'CrysAlisPro, Agilent Technologies'
_computing_data_reduction        'CrysAlisPro, Agilent Technologies'
_computing_molecular_graphics    'XSEED (Barbour, 2001)'
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean 5.3095
_diffrn_measured_fraction_theta_full 0.945
_diffrn_measured_fraction_theta_max 0.928
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0603
_diffrn_reflns_av_unetI/netI     0.0738
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            9545
_diffrn_reflns_theta_full        72.00
_diffrn_reflns_theta_max         73.55
_diffrn_reflns_theta_min         4.55
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_decay_%        0
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.771
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.772
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
; 
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       fragment
_exptl_crystal_F_000             541
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: tetrahydrofuran/methanol'
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.921
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         4773
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1092
_refine_ls_R_factor_gt           0.0815
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1576P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2193
_refine_ls_wR_factor_ref         0.2474
_reflns_number_gt                3374
_reflns_number_total             4773
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c8cc10122a2.cif
_cod_data_source_block           sgctc3
_cod_original_formula_sum        'C30.15 H32.60 O7.15'
_cod_database_code               7122912
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H39 of O39, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H28 of O28, H27 of O27, H17 of O17, H18 of O18, H7 of
  O7, H8 of O8
2. Restrained distances
 H39-H34B
 -2.4 with sigma of 0.02
3. Others
 Fixed Sof: C38(0.15) H38A(0.15) H38B(0.15) H38C(0.15) O39(0.15) H39(0.15)
4.a Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C12(H12), C15(H15), C22(H22), C25(H25)
4.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C20(H20A,H20B,H20C), C30(H30A,H30B,H30C), C32(H32A,H32B,
 H32C), C38(H38A,H38B,H38C)
4.d Idealised tetrahedral OH refined as rotating group:
 O39(H39)
;