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_1560731
_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
'Br4 Cu, C122 H84 F6 N24 Ni4 O6 S2, 4(C F3 O3 S)'
_chemical_formula_sum            'C126 H84 Br4 Cu F18 N24 Ni4 O18 S6'
_chemical_formula_weight         3374.55
_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             2018-07-10
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-20 deposited with the CCDC.	2021-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 119.638(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.6581(8)
_cell_length_b                   19.3004(5)
_cell_length_c                   27.7984(9)
_cell_measurement_reflns_used    22966
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      24.1996989584
_cell_measurement_theta_min      1.21950096102
_cell_volume                     15695.6(8)
_computing_cell_refinement
'XIA2 0.5.542-g41349194-dials-1.9 (Winter, G., 2010)'
_computing_data_collection
'XIA2 0.5.542-g41349194-dials-1.9 (Winter, G., 2010)'
_computing_data_reduction
'XIA2 0.5.542-g41349194-dials-1.9 (Winter, G., 2010)'
_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      120.0
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0617
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            49607
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        18.243
_diffrn_reflns_theta_max         18.243
_diffrn_reflns_theta_min         1.225
_exptl_absorpt_coefficient_mu    1.643
_exptl_absorpt_correction_T_max  1.0
_exptl_absorpt_correction_T_min  0.989
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.428
_exptl_crystal_description       block
_exptl_crystal_F_000             6764
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of diethyl ether and acetonitrile  by vapour diffusion'
_exptl_crystal_size_max          0.118
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.043
_refine_diff_density_max         1.957
_refine_diff_density_min         -1.581
_refine_diff_density_rms         0.192
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.397
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     678
_refine_ls_number_reflns         6192
_refine_ls_number_restraints     747
_refine_ls_restrained_S_all      2.286
_refine_ls_R_factor_all          0.1669
_refine_ls_R_factor_gt           0.1602
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4648
_refine_ls_wR_factor_ref         0.4780
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5165
_reflns_number_total             6192
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00647a2.cif
_cod_data_source_block           8
_cod_depositor_comments
'Adding full bibliography for 1560727--1560734.cif.'
_cod_database_code               1560731
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.830
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 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
 S1-F1 \\sim S1-F2 \\sim S1-F6
 with sigma of 0.04
 S1-O1 \\sim S1-O2 \\sim S1-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
 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
 S6-F3 \\sim S6-F4 \\sim S6-F5
 with sigma of 0.04
 S6-O7 \\sim S6-O8 \\sim S6-O9
 with sigma of 0.02
 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
 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
 S2-F7 \\sim S2-F8 \\sim S2-F9
 with sigma of 0.04
 S2-O4 \\sim S2-O5 \\sim S2-O6
 with sigma of 0.02
 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
3. Uiso/Uaniso restraints and constraints
S1 \\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
S6 \\sim 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
S2 \\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
 S1, F1, F2, F6, O1, O2, O3, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S6, F3, F4, F5, O7, O8, O9, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2, O4, O5, O6, C1C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Ni1, Ni2, N1, C5, C4, C3, C2, C1, N2, N3, N4, N5, N6, N7, N8, N9, N10, N11,
 N12, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20,
 C21, C22, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36,
  C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, C47, C48, C49, C50, C51,
 C52, C53, C54, C55, C56, C57, C58, C59, C60
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Everything fixed:
 S1, F1, F2, F6, O1, O2, O3, C1B, S2, O4, O5, O6, C1C, F7, F8, F9, S6, F3, F4,
 F5, O7, O8, O9, C1A
5.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C3(H3), C2(H2), C1(H1), 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),
  C46(H46), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53), C54(H54),
 C57(H57), C58(H58), C60(H60)
5.c Fitted hexagon refined as free rotating group:
 N1(C5,C4,C3,C2,C1)
;
_shelx_res_checksum              4311
_shelx_hkl_checksum              23242
_shelx_fab_checksum              55899
_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 JV752CuBr
_olex2_submission_special_instructions 'No special instructions were received'