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_1560732
_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 H88 N24 Ni4, 8(C F3 O3 S), 2(C2 H3 N), 8[C2H3N]'
_chemical_formula_sum            'C132 H88 F24 N26 Ni4 O24 S8'
_chemical_formula_weight         3369.60
_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             2020-05-01
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.04.02 svn.r1fbe7b6f for OlexSys, GUI svn.r6076)
;
_audit_update_record
;
2020-08-20 deposited with the CCDC.	2021-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.2627(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.7631(4)
_cell_length_b                   20.3760(3)
_cell_length_c                   26.2656(4)
_cell_measurement_reflns_used    54930
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      75.4250
_cell_measurement_theta_min      3.5520
_cell_volume                     15497.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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   -112.00 -15.00   1.00    5.00    --  -41.67 -57.00  90.00   97
  2  \w    -68.00  28.00   1.00    5.00    --  -41.67  57.00-120.00   96
  3  \w    -64.00  31.00   1.00    5.00    --  -41.67  38.00  30.00   95
  4  \w      1.00  82.00   1.00    5.00    --   41.67 -99.00  30.00   81
  5  \w     57.00 128.00   1.00    5.00    --   41.67 178.00  60.00   71
  6  \w     94.00 178.00   1.00   20.00    --  111.00 125.00 -30.00   84
  7  \w     40.00 135.00   1.00   20.00    --  111.00 -45.00  30.00   95
  8  \w     94.00 178.00   1.00   20.00    --  111.00 125.00 -60.00   84
  9  \w     40.00 135.00   1.00   20.00    --  111.00 -45.00-180.00   95
 10  \w     31.00 156.00   1.00   20.00    --  111.00 -15.00  30.00  125
 11  \w     39.00 121.00   1.00   20.00    --  111.00-125.00-180.00   82
 12  \w     31.00 156.00   1.00   20.00    --  111.00 -15.00-180.00  125
 13  \w     40.00 135.00   1.00   20.00    --  111.00 -45.00  90.00   95
 14  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00  60.00   79
 15  \w     94.00 178.00   1.00   20.00    --  111.00 125.00   0.00   84
 16  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00 -30.00   79
 17  \w     37.00 142.00   1.00   20.00    --  111.00 -77.00-120.00  105
 18  \w     39.00 121.00   1.00   20.00    --  111.00-125.00  60.00   82
 19  \w     87.00 178.00   1.00   20.00    --  111.00  30.00  90.00   91
 20  \w     39.00 121.00   1.00   20.00    --  111.00-125.00 150.00   82
 21  \w     36.00 135.00   1.00   20.00    --  111.00 -30.00 -90.00   99
 22  \w     39.00 121.00   1.00   20.00    --  111.00-125.00-150.00   82
 23  \w     40.00 135.00   1.00   20.00    --  111.00 -45.00-120.00   95
 24  \w     41.00 139.00   1.00   20.00    --  111.00 -61.00 -90.00   98
 25  \w     39.00 121.00   1.00   20.00    --  111.00-125.00 -60.00   82
 26  \w   -112.00 -15.00   1.00    5.00    --  -41.67 -57.00   0.00   97
 27  \w   -112.00 -15.00   1.00    5.00    --  -41.67 -57.00 -90.00   97
 28  \w   -112.00 -15.00   1.00    5.00    --  -41.67 -57.00-180.00   97
 29  \w   -116.00 -10.00   1.00    5.00    --  -41.67 -77.00-120.00  106
 30  \w   -116.00 -10.00   1.00    5.00    --  -41.67 -77.00   0.00  106
 31  \w    -31.00  64.00   1.00    5.00    --   41.67 -38.00  60.00   95
 32  \w     87.00 178.00   1.00   20.00    --  111.00  30.00-150.00   91
 33  \w     83.00 141.00   1.00   20.00    --  111.00  61.00 120.00   58
 34  \w     83.00 178.00   1.00   20.00    --  111.00  61.00  30.00   95
 35  \w     66.00 178.00   1.00   20.00    --  111.00  15.00 -60.00  112
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0507604000
_diffrn_orient_matrix_UB_12      -0.0130184000
_diffrn_orient_matrix_UB_13      0.0109597000
_diffrn_orient_matrix_UB_21      0.0070040000
_diffrn_orient_matrix_UB_22      0.0737916000
_diffrn_orient_matrix_UB_23      -0.0067155000
_diffrn_orient_matrix_UB_31      0.0142572000
_diffrn_orient_matrix_UB_32      0.0101826000
_diffrn_orient_matrix_UB_33      0.0630662000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0786
_diffrn_reflns_av_unetI/netI     0.0279
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            156152
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.348
_diffrn_reflns_theta_min         3.572
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.438
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.665
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.444
_exptl_crystal_description       block
_exptl_crystal_F_000             6840
_exptl_crystal_size_max          0.471
_exptl_crystal_size_mid          0.206
_exptl_crystal_size_min          0.148
_refine_diff_density_max         1.750
_refine_diff_density_min         -4.012
_refine_diff_density_rms         0.192
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.696
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     911
_refine_ls_number_reflns         16138
_refine_ls_number_restraints     216
_refine_ls_restrained_S_all      1.692
_refine_ls_R_factor_all          0.1329
_refine_ls_R_factor_gt           0.1227
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3605
_refine_ls_wR_factor_ref         0.3786
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13435
_reflns_number_total             16138
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00647a2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 1560727--1560734.cif.'
_cod_database_code               1560732
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C120 H84 N24 Ni4 S8 O24 F24'
_chemical_oxdiff_usercomment     '@ 120 K K84'
_shelx_estimated_absorpt_t_max   0.714
_shelx_estimated_absorpt_t_min   0.393
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 S4-O10
 1.44 with sigma of 0.02
 S4-O12
 1.44 with sigma of 0.02
 S4-O11
 1.44 with sigma of 0.02
 S4-C64
 1.85 with sigma of 0.02
 O11-O12
 2.4 with sigma of 0.04
 O12-O10
 2.4 with sigma of 0.04
 O11-O10
 2.4 with sigma of 0.04
 O3-O1
 2.4 with sigma of 0.04
 F1-F3
 2.15 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O10) \\sim Ueq, Uanis(S4) \\sim Ueq, Uanis(O12) \\sim Ueq, Uanis(O11)
\\sim Ueq, Uanis(C64) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F10) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 S1, F1, F2, F3, O1, O2, O3, C61
 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
 S2, F4, F5, F6, O4, O5, O6, C62
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1, O1, O2, O3, C61, F1, F2, F3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2, O4, O5, O6, C62, F4, F5, F6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S3, C63, F7, F8, F9, O7, O8, O9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: F10(0.5) F11(0.5) F12(0.5) O10(0.5) O11(0.5) O12(0.5) S4A(0.5)
 F13(0.5) F14(0.5) F15(0.5) O13(0.5) O14(0.5) O15(0.5) C64A(0.5)
6.a Everything fixed:
 S4, F10, F11, F12, O10, O11, O12, C64, S4A, F13, F14, F15, O13, O14, O15, C64A
6.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)
6.c Idealised Me refined as rotating group:
 C66(H66A,H66B,H66C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              4122
_shelx_hkl_checksum              3553
_shelx_fab_checksum              36751
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_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 1.653
_oxdiff_exptl_absorpt_empirical_full_min 0.663