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_1560733
_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 Fe, 7(C F3 O3 S), 22(C2 H3 N)'
_chemical_formula_sum            'C151 H120 Cl4 F21 Fe N36 Ni4 O21 S7'
_chemical_formula_weight         3830.73
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-12
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.02.02 svn.r3481 for OlexSys, GUI svn.r5470)
;
_audit_update_record
;
2020-08-20 deposited with the CCDC.	2021-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.491(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.6627(5)
_cell_length_b                   20.3859(2)
_cell_length_c                   26.5585(4)
_cell_measurement_reflns_used    111185
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      28.5640
_cell_measurement_theta_min      3.0580
_cell_volume                     15600.4(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_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 -20.00 30.00 1.00 20.00 -- -9.43 -99.00 -60.00 50 2 \w -32.00 63.00 1.00 20.00 -- -9.43 38.00 90.00 95 3 \w -20.00 30.00 1.00 20.00 -- -9.43 -99.00 128.00 50 4 \w -32.00 63.00 1.00 20.00 -- -9.43 38.00 120.00 95 5 \w -49.00 -1.00 1.00 20.00 -- -9.43 99.00-125.00 48 6 \w -88.00 27.00 1.00 20.00 -- -9.43 -19.00 -90.00 115 7 \w -62.00 33.00 1.00 20.00 -- 10.84 -38.00-150.00 95 8 \w -36.00 61.00 1.00 20.00 -- -9.43 57.00 -30.00 97 9 \w -20.00 30.00 1.00 20.00 -- -9.43 -99.00 30.00 50 10 \w -84.00 -38.00 1.00 20.00 -- -9.43 153.00 40.73 46 11 \w -21.00 85.00 1.00 20.00 -- 10.84 77.00-180.00 106 12 \w 0.00 65.00 1.00 20.00 -- 10.84-123.00 -97.06 65 13 \w 7.00 71.00 1.00 20.00 -- 10.84-133.00 85.04 64 14 \w -83.00 -58.00 1.00 20.00 -- -9.43 -77.00 120.00 25 15 \w -20.00 30.00 1.00 20.00 -- -9.43 -99.00-150.00 50 16 \w -20.00 51.00 1.00 20.00 -- 10.84 -99.00 30.00 71 17 \w -6.00 60.00 1.00 20.00 -- 10.84-115.00-147.91 66 18 \w -2.00 63.00 1.00 20.00 -- 10.84-120.00 -13.70 65'
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford DIffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0233678000
_diffrn_orient_matrix_UB_12      0.0088556000
_diffrn_orient_matrix_UB_13      0.0165365000
_diffrn_orient_matrix_UB_21      0.0008141000
_diffrn_orient_matrix_UB_22      -0.0232910000
_diffrn_orient_matrix_UB_23      0.0202282000
_diffrn_orient_matrix_UB_31      0.0077186000
_diffrn_orient_matrix_UB_32      -0.0242819000
_diffrn_orient_matrix_UB_33      -0.0133614000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0552
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            238777
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         2.728
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.833
_exptl_absorpt_correction_T_max  0.9649
_exptl_absorpt_correction_T_min  0.8530
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0831 before and 0.0584 after correction. The Ratio of minimum to maximum transmission is 0.8840. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.631
_exptl_crystal_description       prism
_exptl_crystal_F_000             7812
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of diethyl ether and acetonitrile  by vapour diffusion'
_exptl_crystal_size_max          0.434
_exptl_crystal_size_mid          0.325
_exptl_crystal_size_min          0.289
_refine_diff_density_max         2.054
_refine_diff_density_min         -1.199
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1006
_refine_ls_number_reflns         14267
_refine_ls_number_restraints     197
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0655
_refine_ls_shift/su_max          0.025
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0916P)^2^+118.4251P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1774
_refine_ls_wR_factor_ref         0.1864
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12312
_reflns_number_total             14267
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00647a2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 1560727--1560734.cif.'
_cod_database_code               1560733
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C120 H84 Ni4 S6 O18 F18 Fe Cl4'
_chemical_oxdiff_usercomment     '@ 120 K JV710'
_shelx_estimated_absorpt_t_max   0.795
_shelx_estimated_absorpt_t_min   0.714
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C68-F11 \\sim C68-F10 \\sim C68-F12
 with sigma of 0.02
 F11-F10 \\sim F10-F12 \\sim F12-F11
 with sigma of 0.04
 O10-O11 \\sim O11-O12 \\sim O10-O12
 with sigma of 0.04
 C68-O10 \\sim C68-O11 \\sim C68-O12
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
F10 \\sim F11 \\sim F12 \\sim O10 \\sim O11 \\sim O12 \\sim C68: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 F10, F11, F12, O10, O11, O12, C68
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S4, O10, O11, O12, C68, F10, F11, F12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S3, O7, O8, O9, C67, F7, F8, F9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{S1, F1, F2, F3, O1, O2, O3, C65} sigma for 1-2: 0.02, 1-3: 0.04
as
{S4, F10, F11, F12, O10, O11, O12, C68}
6. Others
 Fixed Sof: S4(0.5) F10(0.5) F11(0.5) F12(0.5) O10(0.5) O11(0.5) O12(0.5)
 C68(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 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),
  C24(H24), C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33),
 C34(H34), C37(H37), C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44),
  C47(H47), C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54),
 C57(H57), C58(H58), C60(H60)
7.b Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C)
;
_shelx_res_checksum              7713
_shelx_hkl_checksum              40203
_shelx_fab_checksum              17179
_olex2_date_sample_data_collection 2018-03-06
_olex2_date_sample_submission    2018-02-02
_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 JV710
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 1.266
_oxdiff_exptl_absorpt_empirical_full_min 0.836