Guest-induced magnetic exchange in paramagnetic [M2L4]4+ coordination cages
Singh, Mukesh K.; Etcheverry-Berríos, Alvaro; Vallejo, Julia; Sanz, Sergio; Martínez-Lillo, José; Nichol, Gary S.; Lusby, Paul J.; Brechin, Euan K.; Dalton Transactions  (2022) –; doi:10.1039/D2DT01385A

data_7710292
_publ_section_title
;
 Guest-induced magnetic exchange in paramagnetic [M2L4]4+ coordination
 cages
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01385A
_journal_year                    2022
_chemical_formula_moiety
'Br6 Re, C82 H48 Cu2 F6 N8 O6 S2, 1.171(C4 H10 O), 1.658(C H3 N O2)'
_chemical_formula_sum            'C88.34 H64.69 Br6 Cu2 F6 N9.66 O10.48 Re S2'
_chemical_formula_weight         2400.12
_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             2022-04-03
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.03.08 svn.r54f81f84 for OlexSys, GUI svn.r6485)
;
_audit_update_record
;
2022-04-03 deposited with the CCDC.	2022-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.7300(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.25190(10)
_cell_length_b                   24.1742(2)
_cell_length_c                   12.27730(10)
_cell_measurement_reflns_used    46662
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      75.8350
_cell_measurement_theta_min      4.0250
_cell_volume                     4526.30(6)
_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 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0
_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   -128.00 -35.00   1.00    5.00    --  -41.67-178.00 -60.00   93
  2  \w    -79.00  37.00   1.00    5.00    --  -41.67  19.00-150.00  116
  3  \w   -128.00 -35.00   1.00    5.00    --  -41.67-178.00 150.00   93
  4  \w   -114.00 -19.00   1.00    5.00    --  -41.67 -38.00  30.00   95
  5  \w     57.00 128.00   1.00    5.00    --   41.67 178.00  60.00   71
  6  \w     10.00 116.00   1.00    5.00    --   41.67  77.00 150.00  106
  7  \w     39.00 121.00   1.00   20.00    --  111.00-125.00 150.00   82
  8  \w     66.00 178.00   1.00   20.00    --  111.00  15.00 -60.00  112
  9  \w     40.00 135.00   1.00   20.00    --  111.00 -45.00-120.00   95
 10  \w     39.00 121.00   1.00   20.00    --  111.00-125.00  90.00   82
 11  \w     80.00 178.00   1.00   20.00    --  111.00  77.00-150.00   98
 12  \w     39.00 121.00   1.00   20.00    --  111.00-125.00  30.00   82
 13  \w     39.00 121.00   1.00   20.00    --  111.00-125.00 -60.00   82
 14  \w     39.00 121.00   1.00   20.00    --  111.00-125.00-120.00   82
 15  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00 -90.00   79
 16  \w     94.00 178.00   1.00   20.00    --  111.00 125.00 -30.00   84
 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     39.00 121.00   1.00   20.00    --  111.00-125.00   0.00   82
 20  \w     39.00 121.00   1.00   20.00    --  111.00-125.00-150.00   82
 21  \w     66.00 178.00   1.00   20.00    --  111.00  15.00  60.00  112
 22  \w     80.00 178.00   1.00   20.00    --  111.00  77.00 -90.00   98
 23  \w     37.00 142.00   1.00   20.00    --  111.00 -77.00  60.00  105
 24  \w     30.00 109.00   1.00   20.00    --  111.00 -94.00-150.00   79
 25  \w     87.00 178.00   1.00   20.00    --  111.00  45.00  60.00   91
 26  \w     37.00 142.00   1.00   20.00    --  111.00 -77.00 -30.00  105
 27  \w     39.00 121.00   1.00   20.00    --  111.00-125.00 -30.00   82
 28  \w     94.00 178.00   1.00   20.00    --  111.00 125.00 -90.00   84
 29  \w     94.00 178.00   1.00   20.00    --  111.00 125.00-150.00   84
 30  \w     87.00 178.00   1.00   20.00    --  111.00  45.00-150.00   91
 31  \w     87.00 178.00   1.00   20.00    --  111.00  45.00 -30.00   91
 32  \w     41.00 139.00   1.00   20.00    --  111.00 -61.00   0.00   98
 33  \w   -116.00 -10.00   1.00    5.00    --  -41.67 -77.00   0.00  106
 34  \w   -116.00 -10.00   1.00    5.00    --  -41.67 -77.00 150.00  106
 35  \w   -116.00 -10.00   1.00    5.00    --  -41.67 -77.00 -90.00  106
 36  \w   -112.00 -15.00   1.00    5.00    --  -41.67 -57.00  30.00   97
 37  \w   -116.00 -10.00   1.00    5.00    --  -41.67 -77.00-120.00  106
 38  \w   -112.00 -15.00   1.00    5.00    --  -41.67 -57.00 150.00   97
 39  \w     87.00 178.00   1.00   20.00    --  111.00  30.00 150.00   91
 40  \w     80.00 176.00   1.00   20.00    --  111.00  77.00   0.00   96
 41  \w     80.00 178.00   1.00   20.00    --  111.00  77.00 150.00   98
 42  \w     83.00 178.00   1.00   20.00    --  111.00  61.00  90.00   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      0.0616349000
_diffrn_orient_matrix_UB_12      -0.0538983000
_diffrn_orient_matrix_UB_13      0.0216520000
_diffrn_orient_matrix_UB_21      0.0269491000
_diffrn_orient_matrix_UB_22      0.0222475000
_diffrn_orient_matrix_UB_23      0.0924020000
_diffrn_orient_matrix_UB_31      -0.1059326000
_diffrn_orient_matrix_UB_32      -0.0257356000
_diffrn_orient_matrix_UB_33      0.0345726000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0659
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            109104
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         76.342
_diffrn_reflns_theta_min         3.426
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.8
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    7.278
_exptl_absorpt_correction_T_max  0.4717
_exptl_absorpt_correction_T_min  0.2481
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1142 before and 0.0835 after correction.
The Ratio of minimum to maximum transmission is 0.5260.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'light brown'
_exptl_crystal_density_diffrn    1.761
_exptl_crystal_description       plate
_exptl_crystal_F_000             2350
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of diethyl ether and nitromethane  by vapour diffusion'
_exptl_crystal_size_max          0.375
_exptl_crystal_size_mid          0.056
_exptl_crystal_size_min          0.043
_refine_diff_density_max         1.603
_refine_diff_density_min         -1.616
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.178
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     564
_refine_ls_number_reflns         9438
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.192
_refine_ls_R_factor_all          0.0686
_refine_ls_R_factor_gt           0.0638
_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^)+(0.0682P)^2^+30.7700P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1708
_refine_ls_wR_factor_ref         0.1747
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8666
_reflns_number_total             9438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01385a2.cif
_cod_data_source_block           eb17063
_cod_database_code               7710292
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C90 H50 Br6 Cu2 F6 N10 O12 Re1 S2'
_chemical_oxdiff_usercomment     '@ 120 K JV484a'
_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
 O301-N301 = O302-N301 = O402-N401 = O401-N401
 1.22 with sigma of 0.02
 N301-C303 = N401-C401
 1.44 with sigma of 0.02
 O201-C203 = O201-C201
 1.41 with sigma of 0.02
 C204-C203 = C202-C201
 1.48 with sigma of 0.02
 O301-O302 = O401-O402
 2.12 with sigma of 0.04
 C303-O301 = C401-O402
 2.28 with sigma of 0.04
 C303-O302 = C401-O401
 2.28 with sigma of 0.04
 C203-C201
 2.36 with sigma of 0.04
 O201-C204
 2.36 with sigma of 0.04
 O201-C202
 2.36 with sigma of 0.04
3. Restrained planarity
 O301, O302, N301, C303
 with sigma of 0.1
 O401, O402, N401, C401
 with sigma of 0.1
4. Others
 Sof(O301)=Sof(O302)=Sof(N301)=Sof(C303)=Sof(H30A)=Sof(H30B)=Sof(H30C)=
 Sof(O401)=Sof(O402)=Sof(N401)=Sof(C401)=Sof(H40A)=Sof(H40B)=Sof(H40C)=1-FVAR(1)
 Sof(O201)=Sof(C201)=Sof(H20A)=Sof(H20B)=Sof(C202)=Sof(H20C)=Sof(H20D)=
 Sof(H20E)=Sof(C203)=Sof(H20F)=Sof(H20G)=Sof(C204)=Sof(H20H)=Sof(H20I)=
 Sof(H20J)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C201(H20A,H20B), C203(H20F,H20G)
5.b Me refined with riding coordinates:
 C202(H20C,H20D,H20E), C204(H20H,H20I,H20J), C303(H30A,H30B,H30C), C401(H40A,
 H40B,H40C)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C9(H9), C10(H10), C11(H11), C13(H13),
 C14(H14), C15(H15), C16(H16), C18(H18), C21(H21), C22(H22), C23(H23), C25(H25),
  C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38)
;
_shelx_res_checksum              41883
_olex2_date_sample_data_collection 2017-05-05
_olex2_date_sample_submission    2017-05-01
_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 JV484a
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 1.845
_oxdiff_exptl_absorpt_empirical_full_min 0.672