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_7710291
_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
'C83 H50 Cu2 F9 N8 O10 S3, C F3 O3 S, C2 H3 N + other solvent'
_chemical_formula_sum            'C86 H53 Cu2 F12 N9 O13 S4'
_chemical_formula_weight         1903.69
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-20
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.07.08 svn.r3312 for OlexSys, GUI svn.r5203)
;
_audit_update_record
;
2017-08-24 deposited with the CCDC.	2022-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                64.740(3)
_cell_angle_beta                 74.232(3)
_cell_angle_gamma                78.345(3)
_cell_formula_units_Z            2
_cell_length_a                   14.0285(6)
_cell_length_b                   19.1152(9)
_cell_length_c                   21.1384(11)
_cell_measurement_reflns_used    4644
_cell_measurement_temperature    200.0
_cell_measurement_theta_max      22.21
_cell_measurement_theta_min      2.22
_cell_volume                     4909.3(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       APEX2
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      200.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker SMART APEXII diffractometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0869
_diffrn_reflns_av_unetI/netI     0.0742
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            47951
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        20.814
_diffrn_reflns_theta_max         20.814
_diffrn_reflns_theta_min         1.089
_diffrn_source                   Mo-tube
_diffrn_source_current           30
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.600
_exptl_absorpt_correction_T_max  0.429
_exptl_absorpt_correction_T_min  0.305
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0746 before and 0.0502 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.0793 before and 0.0507 after correction.
 The Ratio of minimum to maximum transmission is 0.71.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 47951 reflections, Rint = 0.0869
 (11865 with I > 3sig(I), Rint = 0.0460)
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.288
_exptl_crystal_description       block
_exptl_crystal_F_000             1932
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of DCM and acetonitrile by slow evaporation'
_exptl_crystal_size_max          0.358
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.063
_refine_diff_density_max         1.114
_refine_diff_density_min         -0.533
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1321
_refine_ls_number_reflns         13413
_refine_ls_number_restraints     1074
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.1330
_refine_ls_R_factor_gt           0.0991
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1783P)^2^+20.4557P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2639
_refine_ls_wR_factor_ref         0.2909
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9503
_reflns_number_total             13413
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01385a2.cif
_cod_data_source_block           2
_cod_database_code               7710291
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.814
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.551(2) 0.449(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
3. Shared sites
{O7, O7A}
{O11, O11A}
{O12, O12A}
{O4, O4A}
4. 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
5. Uiso/Uaniso restraints and constraints
Uanis(O7) = Uanis(O7A)
Uanis(O11) = Uanis(O11A)
Uanis(O12) = Uanis(O12A)
Uanis(O4) = Uanis(O4A)
6. Rigid body (RIGU) restrains
 S3, S3A, F7, F7A, F8, F8A, F9, F9A, O7, O7A, O8, O8A, O9, O9A, C83, C83A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N91, C91, C92
 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, C82, S2A, F4A, F5A, F6A, O4A, O5A, O6A, C82A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C73, C68
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12, C13
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{S1, F1, F2, F3, O1, O2, O3, C81} sigma for 1-2: 0.02, 1-3: 0.02
as
{S2, F4, F5, F6, O4, O5, O6, C82}
{S1, F1, F2, F3, O1, O2, O3, C81} sigma for 1-2: 0.02, 1-3: 0.02
as
{S2A, F4A, F5A, F6A, O4A, O5A, O6A, C82A}
{S1, F1, F2, F3, O1, O2, O3, C81} sigma for 1-2: 0.02, 1-3: 0.02
as
{S3, F7, F8, F9, O7, O8, O9, C83}
{S1, F1, F2, F3, O1, O2, O3, C81} sigma for 1-2: 0.02, 1-3: 0.02
as
{S3A, F7A, F8A, F9A, O7A, O8A, O9A, C83A}
{S1, F1, F2, F3, O1, O2, O3, C81} sigma for 1-2: 0.02, 1-3: 0.02
as
{S4, F10, F11, F12, O10, O11, O12, C84}
{S1, F1, F2, F3, O1, O2, O3, C81} sigma for 1-2: 0.02, 1-3: 0.02
as
{S4A, F10A, F11A, F12A, O10A, O11A, O12A, C84A}
8. Others
 Sof(S3A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(O7A)=Sof(O8A)=Sof(O9A)=Sof(C83A)=1-
 FVAR(1)
 Sof(S3)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(O7)=Sof(O8)=Sof(O9)=Sof(C83)=FVAR(1)
 Sof(S4A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(O10A)=Sof(O11A)=Sof(O12A)=
 Sof(C84A)=1-FVAR(2)
 Sof(S4)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(O10)=Sof(O11)=Sof(O12)=Sof(C84)=FVAR(2)
 Sof(S2A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=Sof(C82A)=1-
 FVAR(3)
 Sof(S2)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(C82)=FVAR(3)
9.a Rotating group:
 O21(H21A,H21B)
9.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C9(H9), C10(H10), C11(H11), C13(H13),
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25),
  C29(H29), C30(H30), C31(H31), C33(H33), C37(H37), C38(H38), C39(H39),
 C40(H40), C41(H41), C42(H42), C43(H43), C45(H45), C49(H49), C50(H50), C51(H51),
  C53(H53), C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62),
 C63(H63), C65(H65), C69(H69), C70(H70), C71(H71), C73(H73), C77(H77), C78(H78),
  C79(H79), C80(H80)
9.c Idealised Me refined as rotating group:
 C92(H92A,H92B,H92C)
;
_shelx_res_checksum              33333
_shelx_fab_checksum              26175
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-07-17
_olex2_date_sample_submission    2016-07-15
_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 JV178
_olex2_submission_special_instructions 'No special instructions were received'