Sensitive Detection of Spin-Electric Coupling in a Cr3 Antiferromagnetic Triangle
Tacconi, Leonardo; Bisht, Shubham; Cini, Alberto; Perfetti, Mauro; Orlando, Tomas; Fittipaldi, Maria; Shatruk, Michael; Sessoli, Roberta; Chemical Science  (2025) –; doi:10.1039/D5SC08012F

data_1576391
_publ_section_title
;
 Sensitive Detection of Spin-Electric Coupling in a Cr3 Antiferromagnetic
 Triangle
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC08012F
_journal_year                    2025
_chemical_formula_moiety
'C50 H52 Cr3 F3 N7 O15, 7(N O3), C H4 O, 4[CH4O], 9[CH4O]'
_chemical_formula_sum            'C64 H108 Cr3 F3 N14 O50'
_chemical_formula_weight         2086.64
_chemical_properties_physical    Moisture-sensitive,Hygroscopic
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-05
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-10-06 deposited with the CCDC.	2025-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.1530(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.08180(10)
_cell_length_b                   26.5227(2)
_cell_length_c                   28.5781(2)
_cell_measurement_reflns_used    93047
_cell_measurement_temperature    200.0(4)
_cell_measurement_theta_max      75.4260
_cell_measurement_theta_min      3.6700
_cell_volume                     9875.52(13)
_computing_cell_refinement       'CrysAlisPro 1.171.44.104a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 42.100a 64-bit (release 16-08-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.44.104a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.0(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.978
_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    -38.00  25.00   0.50    0.65    --  -47.47  52.00  87.00  126
  2  \w   -119.00 -34.00   0.50    0.65    --  -47.47 -52.00 -58.00  170
  3  \w     34.00 119.00   0.50    0.65    --   47.47  52.00  87.00  170
  4  \w    -24.00  61.00   0.50    0.65    --   47.47 -52.00 -58.00  170
  5  \w   -163.00 -78.00   0.50    2.52    --  -91.75 -52.00 -58.00  170
  6  \w     33.00  80.00   0.50    2.52    --  105.59 -52.00 -58.00   94
  7  \w     92.00 178.00   0.50    2.52    --  105.59  52.00  87.00  172
  8  \w    -45.00  25.00   0.50    0.65    --  -47.47  57.00 -30.00  140
  9  \w      1.00  28.00   0.50    0.65    --  -47.47  19.00-150.00   54
 10  \w    -19.00  26.00   0.50    0.65    --  -47.47  37.00-120.00   90
 11  \w   -119.00 -35.00   0.50    0.65    --  -47.47 -46.00-165.50  168
 12  \w    -27.00  41.00   0.50    0.65    --   47.47 -19.00 -60.00  136
 13  \w     34.00  93.00   0.50    0.65    --   47.47-125.00-180.00  118
 14  \w     82.00 119.00   0.50    0.65    --   47.47  57.00 -90.00   74
 15  \w   -164.00 -20.00   0.50    2.52    --  -91.75   0.00 -90.00  288
 16  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -56.00-132.77  172
 17  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -56.00-107.63  172
 18  \w    -52.00 -19.00   0.50    2.52    --  -91.75  61.00   0.00   66
 19  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -54.00 167.54  172
 20  \w    -85.00 -22.00   0.50    2.52    --  -91.75 125.00  60.00  126
 21  \w   -163.00 -78.00   0.50    2.52    --  -91.75 -49.00 172.37  170
 22  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -54.00-172.51  172
 23  \w   -163.00 -78.00   0.50    2.52    --  -91.75 -51.00 148.58  170
 24  \w   -163.00 -78.00   0.50    2.52    --  -91.75 -49.00-160.32  170
 25  \w    -85.00 -22.00   0.50    2.52    --  -91.75 125.00 150.00  126
 26  \w   -163.00 -82.00   0.50    2.52    --  -91.75 -57.00 150.91  162
 27  \w   -164.00 -20.00   0.50    2.52    --  -91.75   0.00 120.00  288
 28  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -56.00-154.88  172
 29  \w   -161.00 -87.00   0.50    2.52    --  -91.75-125.00-180.00  148
 30  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -56.00 163.78  172
 31  \w   -164.00 -20.00   0.50    2.52    --  -91.75   0.00 -60.00  288
 32  \w   -163.00 -78.00   0.50    2.52    --  -91.75 -52.00-171.63  170
 33  \w     33.00 105.00   0.50    2.52    --  105.59 -94.00 -30.00  144
 34  \w     33.00 105.00   0.50    2.52    --  105.59 -94.00 -60.00  144
 35  \w     34.00  71.00   0.50    2.52    --  105.59 -45.00 -30.00   74
 36  \w     34.00  71.00   0.50    2.52    --  105.59 -45.00 150.00   74
 37  \w     95.00 175.00   0.50    2.52    --  105.59 125.00-180.00  160
 38  \w     34.00  71.00   0.50    2.52    --  105.59 -45.00 120.00   74
 39  \w     33.00  94.00   0.50    2.52    --  105.59 -61.00  90.00  122
 40  \w     93.00 177.00   0.50    2.52    --  105.59  45.00-120.00  168
 41  \w     34.00  71.00   0.50    2.52    --  105.59 -45.00-180.00   74
 42  \w     36.00 111.00   0.50    2.52    --  105.59-125.00  90.00  150
 43  \w     34.00  71.00   0.50    2.52    --  105.59 -45.00  90.00   74
 44  \w     34.00  93.00   0.50    0.65    --   47.47-125.00 -90.00  118
 45  \w     33.00 119.00   0.50    0.65    --   47.47  54.00 159.93  172
 46  \w     33.00 119.00   0.50    0.65    --   47.47  54.00  32.96  172
 47  \w     34.00 119.00   0.50    0.65    --   47.47  52.00-133.84  170
 48  \w     33.00 119.00   0.50    0.65    --   47.47  54.00 -10.10  172
 49  \w     33.00 119.00   0.50    0.65    --   47.47  55.00-174.26  172
 50  \w     33.00 119.00   0.50    0.65    --   47.47  54.00 -51.82  172
 51  \w     33.00 119.00   0.50    0.65    --   47.47  55.00 106.91  172
 52  \w     34.00 119.00   0.50    0.65    --   47.47  53.00-100.94  170
 53  \w     33.00 119.00   0.50    0.65    --   47.47  54.00  55.40  172
 54  \w   -163.00-114.00   0.50    2.52    --  -91.75 -55.00  78.09   98
 55  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -54.00 104.40  172
 56  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -54.00 -18.07  172
 57  \w   -163.00 -78.00   0.50    2.52    --  -91.75 -53.00  46.87  170
 58  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -55.00  33.18  172
 59  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -56.00 -92.47  172
 60  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -56.00  91.74  172
 61  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -56.00 -35.64  172
 62  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -54.00 125.84  172
 63  \w   -163.00 -78.00   0.50    2.52    --  -91.75 -53.00   5.86  170
 64  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -55.00 -80.45  172
 65  \w   -163.00 -77.00   0.50    2.52    --  -91.75 -56.00  65.67  172
 66  \w   -163.00 -78.00   0.50    2.52    --  -91.75 -53.00-124.71  170
 67  \w     36.00 111.00   0.50    2.52    --  105.59-125.00 -90.00  150
 68  \w     33.00 105.00   0.50    2.52    --  105.59 -94.00 150.00  144
 69  \w     33.00 105.00   0.50    2.52    --  105.59 -94.00-120.00  144
 70  \w     34.00  71.00   0.50    2.52    --  105.59 -45.00-150.00   74
 71  \w     33.00 105.00   0.50    2.52    --  105.59 -94.00 120.00  144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0902649000
_diffrn_orient_matrix_UB_12      -0.0353907000
_diffrn_orient_matrix_UB_13      -0.0151884000
_diffrn_orient_matrix_UB_21      -0.0169631000
_diffrn_orient_matrix_UB_22      -0.0094214000
_diffrn_orient_matrix_UB_23      0.0519351000
_diffrn_orient_matrix_UB_31      -0.0744957000
_diffrn_orient_matrix_UB_32      0.0450754000
_diffrn_orient_matrix_UB_33      -0.0011017000
_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  0.0589
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            178672
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.704
_diffrn_reflns_theta_min         3.677
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.598
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.083
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.104a (Rigaku Oxford Diffraction, 2025)
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_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.403
_exptl_crystal_description       block
_exptl_crystal_F_000             4356
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.72
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.439
_refine_diff_density_min         -0.399
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.080(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     979
_refine_ls_number_reflns         19685
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0676
_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^)+(0.1339P)^2^+11.9954P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1887
_refine_ls_wR_factor_ref         0.1969
_reflns_Friedel_coverage         0.933
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.914
_reflns_number_gt                17971
_reflns_number_total             19685
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08012f2.cif
_cod_data_source_block           cr3opaba63cf3pyno37_cc200k
_cod_database_code               1576391
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C58Cr3N14O39F3C70H105Cr3F3N14O45
_chemical_oxdiff_usercomment     'Layer With Ether'
_cell_oxdiff_angle_alpha         89.9768(7)
_cell_oxdiff_angle_beta          95.1269(7)
_cell_oxdiff_angle_gamma         89.9729(7)
_cell_oxdiff_length_a            13.07929(12)
_cell_oxdiff_length_b            26.5259(2)
_cell_oxdiff_length_c            28.5790(2)
_cell_oxdiff_measurement_reflns_used 93072
_cell_oxdiff_volume              9875.55(15)
_shelx_estimated_absorpt_t_max   0.412
_shelx_estimated_absorpt_t_min   0.181
_diffrn_oxdiff_digest_hkl
;
012bf3a3dd637419c0ef4bd7b840f78bb8da48
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.920(6)
 0.080(6)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Restrained distances
 N02W-O02P
 1.23 with sigma of 0.02
 O14-C50
 1.43 with sigma of 0.02
 C1-F2
 1.34 with sigma of 0.02
 C1-F1
 1.34 with sigma of 0.02
 C1-F3
 1.43 with sigma of 0.02
 N02W-O31
 1.23 with sigma of 0.02
 N02W-O34
 1.23 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O31A \\sim O31B: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
5. Others
 Sof(O31B)=1-FVAR(1)
 Sof(O31A)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C44(H44), C45(H45), C31(H31), C9(H9), C30(H30), C34(H34), C27(H27), C41(H41),
 C12(H12), C2(H2), C23(H23), C26(H26), C10(H10), C13(H13), C38(H38), C37(H37),
 C33(H33), C24(H24), C5(H5), C47(H47), C48(H48), C17(H17), C6(H6), C16(H16),
 C4(H4), C19(H19), C20(H20), C40(H40)
6.b Idealised Me refined as rotating group:
 N3(H3A,H3B,H3C), N5(H5A,H5B,H5C), N2(H2A,H2B,H2C), N4(H4A,H4B,H4C), N6(H6A,
 H6B,H6C), N1(H1A,H1B,H1C), C51(H51A,H51B,H51C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C)
6.c Idealised tetrahedral OH refined as rotating group:
 O02J(H02J)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 904 electrons were 
found in a volume of 3692\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
13 [CH4O] 960 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              16362
_shelx_fab_checksum              7154
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.371
_oxdiff_exptl_absorpt_empirical_full_min 0.650