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_1560727
_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 Co, C120 H84 N24 Ni4, 4(C F3 O3 S), 3(C2 H3 N)'
_chemical_formula_sum            'C130 H93 Br4 Co F12 N27 Ni4 O12 S4'
_chemical_formula_weight         3194.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2020-08-15 deposited with the CCDC.	2021-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.013(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.1965(6)
_cell_length_b                   18.5947(3)
_cell_length_c                   28.7563(6)
_cell_measurement_reflns_used    131584
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.8560
_cell_measurement_theta_min      1.6460
_cell_volume                     15673.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.34b (Rigaku OD, 2017)'
_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_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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    -84.00  94.00   0.50   17.00    --    5.00   7.00-130.00  356
  2  \w    -84.00  94.00   0.50   17.00    --    5.00  -7.00  52.00  356
  3  \w   -104.00  75.00   0.50   17.00    --  -14.80   7.00-130.00  358
  4  \w   -104.00  75.00   0.50   17.00    --  -14.80  -7.00  52.00  358
  5  \w   -104.00  26.00   0.50   17.00    --  -14.80 -70.00  90.00  260
  6  \w   -104.00  23.00   0.50   17.00    --  -14.80 -57.00 -60.00  254
  7  \w    -75.00  75.00   0.50   17.00    --  -14.80  38.00-120.00  300
  8  \w    -55.00  75.00   0.50   17.00    --  -14.80  70.00 -30.00  260
  9  \w   -104.00  26.00   0.50   17.00    --  -14.80 -70.00-180.00  260
 10  \w    -55.00  75.00   0.50   17.00    --  -14.80  70.00  90.00  260
 11  \w    -55.00  75.00   0.50   17.00    --  -14.80  70.00 -90.00  260
 12  \w    -55.00  75.00   0.50   17.00    --  -14.80  70.00  30.00  260
 13  \w   -104.00  26.00   0.50   17.00    --  -14.80 -70.00 -90.00  260
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0017956000
_diffrn_orient_matrix_UB_12      0.0380325000
_diffrn_orient_matrix_UB_13      -0.0005188000
_diffrn_orient_matrix_UB_21      0.0014970000
_diffrn_orient_matrix_UB_22      0.0003991000
_diffrn_orient_matrix_UB_23      -0.0240641000
_diffrn_orient_matrix_UB_31      -0.0240708000
_diffrn_orient_matrix_UB_32      -0.0028137000
_diffrn_orient_matrix_UB_33      -0.0104928000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0697
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            670814
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.494
_diffrn_reflns_theta_min         1.615
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.723
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87268
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.34b (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light green'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.354
_exptl_crystal_description       block
_exptl_crystal_F_000             6436
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.680
_refine_diff_density_min         -1.077
_refine_diff_density_rms         0.098
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1750
_refine_ls_number_reflns         35971
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.1120
_refine_ls_R_factor_gt           0.0744
_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^)+(0.0420P)^2^+83.5575P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1485
_refine_ls_wR_factor_ref         0.1673
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23303
_reflns_number_total             35971
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00647a2.cif
_cod_data_source_block           2018ncs0256a
_cod_depositor_comments
'Adding full bibliography for 1560727--1560734.cif.'
_cod_database_code               1560727
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C130 H93 Br4 Co F12 N27 Ni4 O12 S4'
_chemical_oxdiff_usercomment     JV718
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.782
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13),
 C14(H14), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23),
  C24(H24), C27(H27), C28(H28), C30(H30), C31(H31), C33(H33), C34(H34),
 C37(H37), C38(H38), C39(H39), 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), C61(H61), C63(H63), C64(H64), C67(H67), C68(H68),
  C69(H69), C70(H70), C71(H71), C72(H72), C73(H73), C74(H74), C77(H77),
 C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84), C87(H87), C88(H88),
  C90(H90), C91(H91), C93(H93), C94(H94), C97(H97), C98(H98), C99(H99),
 C100(H100), C101(H101), C102(H102), C103(H103), C104(H104), C107(H107),
 C108(H108), C110(H110), C111(H111), C112(H112), C113(H113), C114(H114),
 C117(H117), C118(H118), C120(H120)
2.b Idealised Me refined as rotating group:
 C126(H12A,H12B,H12C), C128(H12D,H12E,H12F), C130(H13A,H13B,H13C)
;
_shelx_res_checksum              56671
_shelx_hkl_checksum              42711
_shelx_fab_checksum              85482
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_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 2.207
_oxdiff_exptl_absorpt_empirical_full_min 0.563