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_1560730
_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
'Br2 Fe0.5, C120 H84 N24 Ni4, 3.5(C2 F6 O6 S2), 2.5(C8 H16 O2), C0.5 F3 O3 S0.5'
_chemical_formula_sum            'C147.5 H124 Br2 F24 Fe0.5 N24 Ni4 O29 S7.5'
_chemical_formula_weight         3815.73
_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             2019-11-29
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2020-08-20 deposited with the CCDC.	2021-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.8120(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.3026(3)
_cell_length_b                   20.5660(2)
_cell_length_c                   26.4213(3)
_cell_measurement_reflns_used    66668
_cell_measurement_temperature    120
_cell_measurement_theta_max      27.4410
_cell_measurement_theta_min      3.6410
_cell_volume                     15678.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120
_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    -60.00  36.00   1.00   30.00    --   10.68 -51.00-123.00   96
  2  \w    -15.00  81.00   1.00   30.00    --   10.68  51.00  21.00   96
  3  \w    -41.00  21.00   1.00   30.00    --   -9.43  77.00 120.00   62
  4  \w    -15.00  30.00   1.00   30.00    --   -9.43 -99.00   0.00   45
  5  \w    -15.00  30.00   1.00   30.00    --   -9.43 -99.00  90.00   45
  6  \w    -42.00  42.00   1.00   30.00    --   10.68 -77.00-150.00   84
  7  \w    -42.00  42.00   1.00   30.00    --   10.68 -77.00 -90.00   84
  8  \w    -15.00  51.00   1.00   30.00    --   10.68 -99.00 150.00   66
  9  \w    -82.00  13.00   1.00   30.00    --   -9.43 -38.00  90.00   95
 10  \w    -80.00  17.00   1.00   30.00    --   -9.43 -57.00-180.00   97
 11  \w    -42.00  22.00   1.00   30.00    --   -9.43 -77.00-150.00   64
 12  \w    -15.00  51.00   1.00   30.00    --   10.68 -99.00 -60.00   66
 13  \w    -15.00  51.00   1.00   30.00    --   10.68 -99.00  60.00   66
 14  \w    -15.00  51.00   1.00   30.00    --   10.68 -99.00  30.00   66
 15  \w    -62.00  33.00   1.00   30.00    --   10.68 -38.00   0.00   95
 16  \w    -15.00  10.00   1.00   30.00    --   -9.43 -99.00  30.00   25
 17  \w    -15.00  51.00   1.00   30.00    --   10.68 -99.00  90.00   66
;
_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      0.0097830000
_diffrn_orient_matrix_UB_12      -0.0281292000
_diffrn_orient_matrix_UB_13      -0.0067862000
_diffrn_orient_matrix_UB_21      -0.0119689000
_diffrn_orient_matrix_UB_22      -0.0198642000
_diffrn_orient_matrix_UB_23      0.0121317000
_diffrn_orient_matrix_UB_31      -0.0191135000
_diffrn_orient_matrix_UB_32      -0.0019636000
_diffrn_orient_matrix_UB_33      -0.0255884000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0536
_diffrn_reflns_av_unetI/netI     0.0206
_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       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            242243
_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         25.682
_diffrn_reflns_theta_min         3.197
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.236
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90404
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.616
_exptl_crystal_description       block
_exptl_crystal_F_000             7760
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of adetonitrile and THF  by vapour diffusion'
_exptl_crystal_size_max          0.271
_exptl_crystal_size_mid          0.201
_exptl_crystal_size_min          0.179
_refine_diff_density_max         2.714
_refine_diff_density_min         -1.114
_refine_diff_density_rms         0.135
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1179
_refine_ls_number_reflns         14855
_refine_ls_number_restraints     656
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0820
_refine_ls_R_factor_gt           0.0729
_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^)+(0.1040P)^2^+173.7598P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2032
_refine_ls_wR_factor_ref         0.2106
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12951
_reflns_number_total             14855
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00647a2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1560727--1560734.cif.'
_cod_original_formula_sum
'C147.50 H124 Br2 F24 Fe0.50 N24 Ni4 O29 S7.50'
_cod_database_code               1560730
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C528 H416 Br16 F72 Fe8 N132 Ni12 O88 S24 '
_chemical_oxdiff_usercomment     '@ 120 K A2_466 FeBr4'
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.63
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C72-C71 \\sim C71-C70 \\sim C70-C69
 with sigma of 0.02
 O14-C72 \\sim O14-C69
 with sigma of 0.02
 O14-C71 \\sim O14-C70
 with sigma of 0.04
 C71-C69 \\sim C72-C70
 with sigma of 0.04
 C68-C67 \\sim C67-C66 \\sim C66-C65
 with sigma of 0.02
 O13-C68 \\sim O13-C65
 with sigma of 0.02
 O13-C67 \\sim O13-C66
 with sigma of 0.04
 C67-C65 \\sim C68-C66
 with sigma of 0.04
 C68-C65 \\sim C69-C72
 with sigma of 0.02
 C1A-F13 \\sim C1A-F14 \\sim C1A-F15
 with sigma of 0.02
 F13-F14 \\sim F14-F15 \\sim F15-F13
 with sigma of 0.04
 S6-F13 \\sim S6-F14 \\sim S6-F15
 with sigma of 0.04
 S6-O16 \\sim S6-O17 \\sim S6-O18
 with sigma of 0.02
 O16-O17 \\sim O17-O18 \\sim O16-O18
 with sigma of 0.04
 C1A-O16 \\sim C1A-O17 \\sim C1A-O18
 with sigma of 0.04
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O14 \\sim C69 \\sim C70 \\sim C71 \\sim C72: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O13 \\sim C65 \\sim C66 \\sim C67 \\sim C68: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C74 \\sim C75: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C1A \\sim F13 \\sim F14 \\sim F15 \\sim S6 \\sim O16 \\sim O17 \\sim O18:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C1A) = Uanis(S6)
5. Rigid body (RIGU) restrains
 O14, C69, C70, C71, C72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, C65, C66, C67, C68
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C74, C75
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, F13, F14, F15, S6, O16, O17, O18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S6, C1A, F13, F14, F15, O16, O17, O18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{O14, C69, C70, C71, C72} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O15, C73, C74, C75, C76}
7. Others
 Fixed Sof: Br1(0.5) Br2(0.5) Fe1(0.25) S4(0.5) F10(0.5) F11(0.5) F12(0.5)
 O10(0.5) O11(0.5) O12(0.5) C64(0.5) O13(0.5) C65(0.5) H65A(0.5) H65B(0.5)
 C66(0.5) H66A(0.5) H66B(0.5) C67(0.5) H67A(0.5) H67B(0.5) C68(0.5) H68A(0.5)
 H68B(0.5) C1A(0.25) F13(0.5) F14(0.5) F15(0.5) S6(0.25) O16(0.5) O17(0.5)
 O18(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,
 H69B), C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B),
 C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B)
8.b 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)
;
_shelx_res_checksum              78278
_shelx_hkl_checksum              97722
_olex2_date_sample_data_collection 2019-10-30
_olex2_date_sample_submission    2019-10-29
_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 'A2_446 FeBr4'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.211
_oxdiff_exptl_absorpt_empirical_full_min 0.877