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_1560734
_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
'Cl4 Co, C120 H84 N24 Ni4, 6(C F3 O3 S), C4 H8 O, 4(C2 H3 N)'
_chemical_formula_sum            'C138 H105 Cl4 Co F18 N28 Ni4 O19 S6'
_chemical_formula_weight         3429.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-09-30
_audit_creation_method
;
Olex2 1.2
(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                 91.1568(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.4016(3)
_cell_length_b                   29.7181(6)
_cell_length_c                   26.8106(6)
_cell_measurement_reflns_used    55397
_cell_measurement_temperature    250.00(10)
_cell_measurement_theta_max      75.1030
_cell_measurement_theta_min      3.3700
_cell_volume                     16251.9(5)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      250.00(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 1.000
_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   10.00    --  -41.92 -57.00 120.00   97
  2  \w    -69.00  28.00   1.00   10.00    --  -41.92  57.00 -90.00   97
  3  \w   -116.00 -11.00   1.00   10.00    --  -41.92 -77.00 -90.00  105
  4  \w   -128.00 -34.00   1.00   10.00    --  -41.92 178.00-180.00   94
  5  \w    -64.00  31.00   1.00   10.00    --  -41.92  38.00  60.00   95
  6  \w      1.00  82.00   1.00   10.00    --   41.92 -99.00  30.00   81
  7  \w     39.00 121.00   1.00   30.00    --  111.00-125.00-120.00   82
  8  \w     87.00 178.00   1.00   30.00    --  111.00  45.00  60.00   91
  9  \w     41.00 139.00   1.00   30.00    --  111.00 -61.00 150.00   98
 10  \w     39.00 121.00   1.00   30.00    --  111.00-125.00 120.00   82
 11  \w     94.00 178.00   1.00   30.00    --  111.00 125.00   0.00   84
 12  \w     94.00 178.00   1.00   30.00    --  111.00 125.00 -90.00   84
 13  \w     39.00 121.00   1.00   30.00    --  111.00-125.00 -30.00   82
 14  \w     37.00 142.00   1.00   30.00    --  111.00 -77.00 -60.00  105
 15  \w     39.00 121.00   1.00   30.00    --  111.00-125.00 150.00   82
 16  \w     39.00 121.00   1.00   30.00    --  111.00-125.00  30.00   82
 17  \w     31.00 156.00   1.00   30.00    --  111.00 -15.00  60.00  125
 18  \w     39.00 121.00   1.00   30.00    --  111.00-125.00 -60.00   82
 19  \w     87.00 178.00   1.00   30.00    --  111.00  45.00-120.00   91
 20  \w     94.00 178.00   1.00   30.00    --  111.00 125.00 -60.00   84
 21  \w     66.00 178.00   1.00   30.00    --  111.00  15.00   0.00  112
 22  \w     41.00 139.00   1.00   30.00    --  111.00 -61.00 -60.00   98
 23  \w     30.00 109.00   1.00   30.00    --  111.00 -94.00  30.00   79
 24  \w     83.00 178.00   1.00   30.00    --  111.00  63.00-133.11   95
 25  \w     30.00 109.00   1.00   30.00    --  111.00 -94.00-180.00   79
 26  \w     40.00 135.00   1.00   30.00    --  111.00 -45.00-120.00   95
 27  \w     39.00 121.00   1.00   30.00    --  111.00-125.00-180.00   82
 28  \w     94.00 178.00   1.00   30.00    --  111.00 125.00  90.00   84
 29  \w     41.00 126.00   1.00   30.00    --  111.00-135.00-175.00   85
 30  \w     31.00 156.00   1.00   30.00    --  111.00 -15.00-120.00  125
 31  \w   -116.00 -11.00   1.00   10.00    --  -41.92 -77.00   0.00  105
 32  \w   -112.00 -15.00   1.00   10.00    --  -41.92 -57.00   0.00   97
 33  \w   -116.00 -11.00   1.00   10.00    --  -41.92 -77.00-180.00  105
 34  \w   -115.00 -19.00   1.00   10.00    --  -41.92 -38.00-120.00   96
 35  \w   -116.00 -11.00   1.00   10.00    --  -41.92 -77.00  90.00  105
 36  \w    -28.00  69.00   1.00   10.00    --   41.92 -57.00 120.00   97
 37  \w     66.00 178.00   1.00   30.00    --  111.00  15.00 150.00  112
 38  \w     83.00 178.00   1.00   30.00    --  111.00  61.00 120.00   95
 39  \w     82.00 178.00   1.00   30.00    --  111.00  66.00 -33.52   96
 40  \w     83.00 178.00   1.00   30.00    --  111.00  61.00 150.00   95
 41  \w     83.00 178.00   1.00   30.00    --  111.00  63.00 -16.29   95
 42  \w     81.00 178.00   1.00   30.00    --  111.00  70.00   0.02   97
 43  \w     80.00 178.00   1.00   30.00    --  111.00  77.00-170.63   98
 44  \w     80.00 178.00   1.00   30.00    --  111.00  77.00  60.00   98
 45  \w     80.00 178.00   1.00   30.00    --  111.00  77.00-120.00   98
 46  \w     83.00 178.00   1.00   30.00    --  111.00  61.00 -90.00   95
 47  \w     83.00 178.00   1.00   30.00    --  111.00  61.00  30.00   95
 48  \w     82.00 178.00   1.00   30.00    --  111.00  67.00  90.61   96
 49  \w     81.00 178.00   1.00   30.00    --  111.00  72.00 -65.55   97
 50  \w     82.00 178.00   1.00   30.00    --  111.00  67.00  53.61   96
 51  \w     80.00 178.00   1.00   30.00    --  111.00  77.00 -90.00   98
 52  \w     80.00 178.00   1.00   30.00    --  111.00  75.00 146.19   98
 53  \w     83.00 178.00   1.00   30.00    --  111.00  61.00-180.00   95
;
_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      0.0061629000
_diffrn_orient_matrix_UB_12      0.0404267000
_diffrn_orient_matrix_UB_13      0.0358001000
_diffrn_orient_matrix_UB_21      -0.0095254000
_diffrn_orient_matrix_UB_22      0.0324642000
_diffrn_orient_matrix_UB_23      -0.0443508000
_diffrn_orient_matrix_UB_31      -0.0746258000
_diffrn_orient_matrix_UB_32      -0.0008057000
_diffrn_orient_matrix_UB_33      0.0074739000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1547
_diffrn_reflns_av_unetI/netI     0.0463
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            294893
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        50.434
_diffrn_reflns_theta_max         50.434
_diffrn_reflns_theta_min         3.297
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.379
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.598
_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            'dark green'
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_description       block
_exptl_crystal_F_000             6984
_exptl_crystal_size_max          0.245
_exptl_crystal_size_mid          0.165
_exptl_crystal_size_min          0.093
_refine_diff_density_max         2.007
_refine_diff_density_min         -1.557
_refine_diff_density_rms         0.154
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.712
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1962
_refine_ls_number_reflns         17006
_refine_ls_number_restraints     2169
_refine_ls_restrained_S_all      1.637
_refine_ls_R_factor_all          0.1392
_refine_ls_R_factor_gt           0.1312
_refine_ls_shift/su_max          0.002
_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          0.3722
_refine_ls_wR_factor_ref         0.3828
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14654
_reflns_number_total             17006
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00647a2.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 1560727--1560734.cif.'
_cod_database_code               1560734
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C120 H84 Ni4 N24 C6 F18 O10 Co Cl4'
_chemical_oxdiff_usercomment     '@ 120 K JV646'
_shelx_estimated_absorpt_t_max   0.744
_shelx_estimated_absorpt_t_min   0.492
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C130-C129 \\sim C129-C128 \\sim C128-C127
 with sigma of 0.02
 O19-C130 \\sim O19-C127
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{S1, F1, F2, F3, O1, O2, O3, C121} sigma for 1-2: 0.02, 1-3: 0.04
as
{S2, F4, F5, F6, O4, O5, O6, C122}
{S1, F1, F2, F3, O1, O2, O3, C121} sigma for 1-2: 0.02, 1-3: 0.04
as
{S3, F7, F8, F9, O7, O8, O9, C123}
{S1, F1, F2, F3, O1, O2, O3, C121} sigma for 1-2: 0.02, 1-3: 0.04
as
{S4, F10, F11, F12, O10, O11, O12, C124}
{S1, F1, F2, F3, O1, O2, O3, C121} sigma for 1-2: 0.02, 1-3: 0.04
as
{S5, F13, F14, F15, O13, O14, O15, C125}
{S1, F1, F2, F3, O1, O2, O3, C121} sigma for 1-2: 0.02, 1-3: 0.04
as
{S6, F16, F17, F18, O16, O17, O18, C126}
{N31, C131, C132} sigma for 1-2: 0.02, 1-3: 0.04
as
{N32, C133, C134}
{N31, C131, C132} sigma for 1-2: 0.02, 1-3: 0.04
as
{N33, C135, C136}
{N31, C131, C132} sigma for 1-2: 0.02, 1-3: 0.04
as
{N34, C137, C138}
6.a Secondary CH2 refined with riding coordinates:
 C127(H12A,H12B), C128(H12C,H12D), C129(H12E,H12F), C130(H13A,H13B)
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), C16(H16), C18(H18), C19(H19), 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), C61(H61), C62(H62), C63(H63), C64(H64), C67(H67),
  C68(H68), 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), C92(H92), C93(H93), C94(H94), C97(H97), C98(H98),
 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)
6.c Idealised Me refined as rotating group:
 C132(H13C,H13D,H13E), C134(H13F,H13G,H13H), C136(H13I,H13J,H13K), C138(H13L,
 H13M,H13N)
;
_shelx_res_checksum              37981
_shelx_hkl_checksum              23098
_shelx_fab_checksum              36662
_olex2_date_sample_data_collection 2018-01-19
_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_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 1.325
_oxdiff_exptl_absorpt_empirical_full_min 0.682