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_1560728
_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 Ni, 6(C F3 O3 S), 22(C2 H3 N)'
_chemical_formula_sum            'C154 H126 Cl4 F18 N38 Ni5 O18 S6'
_chemical_formula_weight         3766.63
_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             2018-05-17
_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                 114.7730(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.8614(3)
_cell_length_b                   20.2670(2)
_cell_length_c                   26.4739(3)
_cell_measurement_reflns_used    39935
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      31.4844683902
_cell_measurement_theta_min      0.815950771407
_cell_volume                     15521.9(3)
_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 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  0.0404
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_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            94775
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.415
_diffrn_reflns_theta_max         24.518
_diffrn_reflns_theta_min         1.189
_exptl_absorpt_coefficient_mu    0.781
_exptl_absorpt_correction_T_max  1.0
_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 green'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.612
_exptl_crystal_description       irregular
_exptl_crystal_F_000             7704
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of acetonitrile and diethyl ether  by vapour diffusion'
_exptl_crystal_size_max          0.046
_exptl_crystal_size_mid          0.042
_exptl_crystal_size_min          0.025
_refine_diff_density_max         1.992
_refine_diff_density_min         -2.231
_refine_diff_density_rms         0.176
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   3.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     990
_refine_ls_number_reflns         14171
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      3.078
_refine_ls_R_factor_all          0.1396
_refine_ls_R_factor_gt           0.1274
_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          0.3680
_refine_ls_wR_factor_ref         0.3778
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11094
_reflns_number_total             14171
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00647a2.cif
_cod_data_source_block           7
_cod_depositor_comments
'Adding full bibliography for 1560727--1560734.cif.'
_cod_database_code               1560728
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.965
_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
 N15-C68 = N13-C64 = N14-C66
 1.14 with sigma of 0.02
 C67-C66 = C65-C64 = C69-C68
 1.46 with sigma of 0.02
 C69-N15 = N13-C65 = N14-C67
 2.6 with sigma of 0.04
3. Rigid body (RIGU) restrains
 N15, C68, C69
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N14, C66, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N13, C64, C65
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S3, F7, F8, F9, O7, O8, O9, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{S1, F1, F2, F3, O1, O2, O3, C61} sigma for 1-2: 0.02, 1-3: 0.04
as
{S3, F7, F8, F9, O7, O8, O9, C63}
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C6(H6), C8(H8), C9(H9), 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),
  C46(H46), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53), C54(H54),
 C57(H57), C58(H58), C60(H60)
5.b Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C)
;
_shelx_res_checksum              92395
_shelx_hkl_checksum              58585
_shelx_fab_checksum              21217
_platon_squeeze_void_probe_radius 1.20
_olex2_date_sample_data_collection 2018-04-20
_olex2_date_sample_submission    2018-03-30
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id JV757
_olex2_submission_special_instructions 'No special instructions were received'