Exploiting host‒guest chemistry to manipulate magnetic interactions in metallosupramolecular M4L6 tetrahedral cages
Scott, Aaron J.; Vallejo, Julia; Sarkar, Arup; Smythe, Lucy; Regincós Martí, E.; Nichol, Gary S.; Klooster, Wim T.; Coles, Simon J.; Murrie, Mark; Rajaraman, Gopalan; Piligkos, Stergios; Lusby, Paul J.; Brechin, Euan K.; Chemical Science 12 (2021) 5134–5142; doi:10.1039/D1SC00647A

data_1560729
_publ_section_title
;
 Exploiting host--guest chemistry to manipulate magnetic interactions in
 metallosupramolecular M4L6 tetrahedral cages
;
_journal_issue                   14
_journal_name_full               'Chemical Science'
_journal_page_first              5134
_journal_page_last               5142
_journal_paper_doi               10.1039/D1SC00647A
_journal_volume                  12
_journal_year                    2021
_chemical_formula_moiety         'C120 H84 N24 Ni4, Cl4 Mn, 6(C F3 O3 S)'
_chemical_formula_sum            'C126 H84 Cl4 F18 Mn N24 Ni4 O18 S6'
_chemical_formula_weight         3188.11
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-05-11
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2020-08-20 deposited with the CCDC.	2021-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.807(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   32.5915(13)
_cell_length_b                   19.6893(7)
_cell_length_c                   26.8651(12)
_cell_measurement_reflns_used    18495
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      34.7277047687
_cell_measurement_theta_min      1.19430644089
_cell_volume                     15386.7(11)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Diamond Light Source Beamline I19-1'
_diffrn_measurement_method       'shutterless scans'
_diffrn_radiation_monochromator  'Silicon 111'
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.1060
_diffrn_reflns_av_unetI/netI     0.0422
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            29061
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        15.363
_diffrn_reflns_theta_max         15.363
_diffrn_reflns_theta_min         1.210
_exptl_absorpt_coefficient_mu    0.751
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.96
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
CCP4 7.0.052: AIMLESS, version 0.6.2 : 15/01/18
Scaling & analysis of unmerged intensities, absorption correction using spherical harmonics
;
_exptl_crystal_colour            'light brown'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.376
_exptl_crystal_description       block
_exptl_crystal_F_000             6460
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of acetonitrile and diethyl ether  by vapour diffusion'
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.038
_refine_diff_density_max         2.727
_refine_diff_density_min         -2.141
_refine_diff_density_rms         0.288
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   5.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     402
_refine_ls_number_reflns         3672
_refine_ls_number_restraints     77
_refine_ls_restrained_S_all      5.014
_refine_ls_R_factor_all          0.2527
_refine_ls_R_factor_gt           0.2397
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.5481
_refine_ls_wR_factor_ref         0.5660
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3008
_reflns_number_total             3672
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00647a2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 1560727--1560734.cif.'
_cod_database_code               1560729
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.949
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 S3-O5 = S3-O4 = S3-O6
 1.48 with sigma of 0.02
 F7-F9
 2.33 with sigma of 0.04
 F9-F8
 2.33 with sigma of 0.04
 F8-F7
 2.33 with sigma of 0.04
 F3-F4
 2.33 with sigma of 0.04
 F3-F5
 2.33 with sigma of 0.04
 F5-F4
 2.33 with sigma of 0.04
 S3-F7
 2.54 with sigma of 0.04
 S3-F8
 2.54 with sigma of 0.04
 S3-F9
 2.54 with sigma of 0.04
 C1A-F3 \\sim C1A-F4 \\sim C1A-F5
 with sigma of 0.02
 F3-F4 \\sim F4-F5 \\sim F5-F3
 with sigma of 0.04
 O7-O8 \\sim O8-O9 \\sim O7-O9
 with sigma of 0.04
 C1A-O7 \\sim C1A-O8 \\sim C1A-O9
 with sigma of 0.04
 C1B-F1 \\sim C1B-F2 \\sim C1B-F6
 with sigma of 0.02
 F1-F2 \\sim F2-F6 \\sim F6-F1
 with sigma of 0.04
 S6-F1 \\sim S6-F2 \\sim S6-F6
 with sigma of 0.04
 S6-O1 \\sim S6-O2 \\sim S6-O3
 with sigma of 0.02
 O1-O2 \\sim O2-O3 \\sim O1-O3
 with sigma of 0.04
 C1B-O1 \\sim C1B-O2 \\sim C1B-O3
 with sigma of 0.04
 C1C-F7 \\sim C1C-F8 \\sim C1C-F9
 with sigma of 0.02
 F7-F8 \\sim F8-F9 \\sim F9-F7
 with sigma of 0.04
 O4-O5 \\sim O5-O6 \\sim O4-O6
 with sigma of 0.04
 C1C-O4 \\sim C1C-O5 \\sim C1C-O6
 with sigma of 0.04
 C55-C54 \\sim C16-C15
 with sigma of 0.02
 C51-C51_$2 \\sim C16-C15
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F3 \\sim F4 \\sim F5 \\sim O7 \\sim O8 \\sim O9 \\sim C1A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
S6 \\sim F1 \\sim F2 \\sim F6 \\sim O1 \\sim O2 \\sim O3 \\sim C1B: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
F7 \\sim F8 \\sim F9 \\sim O4 \\sim O5 \\sim O6 \\sim C1C: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Fixed occupancy and ADP/Uiso:
 S1, F3, F4, F5, O7, O8, O9, C1A, S3, F7, F8, F9, O4, O5, O6, C1C, S6, F1, F2,
 F6, O1, O2, O3, C1B
5.b Aromatic/amide H refined with riding coordinates:
 C00J(H00J), C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C10(H10),
 C11(H11), C12(H12), C13(H13), C14(H14), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C26(H26), C27(H27), C29(H29), C30(H30), C31(H31),
 C32(H32), C33(H33), C36(H36), C37(H37), C39(H39), C40(H40), C42(H42), C43(H43),
  C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), C52(H52), C53(H53),
 C56(H56), C57(H57), C58(H58), C59(H59)
;
_shelx_res_checksum              94497
_shelx_hkl_checksum              49449
_shelx_fab_checksum              97397
_platon_squeeze_void_probe_radius 1.20
_olex2_date_sample_data_collection 2018-04-20
_olex2_date_sample_submission    2018-04-05
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil.'
_olex2_submission_original_sample_id JV753
_olex2_submission_special_instructions 'No special instructions were received'