Macrocyclic transition-metal parashift complexes for MRI at clinical and pre-clinical magnetic fields.
Rogers, Nicola J.; Ashok Kumar, Chowan; Alexander, Carlson; Bowdery, Daniel; Pavlovskaya, Galina; Harvey, Peter; Dalton transactions (Cambridge, England : 2003) 54 (2025) 11036–11046; doi:10.1039/d5dt01149c

data_7718955
_publ_section_title
;
 Macrocyclic transition-metal parashift complexes for MRI at clinical and
 pre-clinical magnetic fields.
;
_journal_issue                   28
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11036
_journal_page_last               11046
_journal_paper_doi               10.1039/d5dt01149c
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C48 H72 Co N8, Cl4 Co, C O'
_chemical_formula_sum            'C49 H72 Cl4 Co2 N8 O'
_chemical_formula_weight         1048.80
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-19
_audit_creation_method
;
Olex2 1.5-ac5-023
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-04-24 deposited with the CCDC.	2025-06-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.6184(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.70786(8)
_cell_length_b                   31.0143(3)
_cell_length_c                   16.12782(14)
_cell_measurement_reflns_used    49158
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      79.6500
_cell_measurement_theta_min      2.8060
_cell_volume                     5246.26(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-023 (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      100(2)
_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 0.991
_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   -121.00 -54.00   0.50    2.50    --  -48.17-153.00 119.00  134
  2  \w   -105.00 -27.00   0.50    2.50    --  -48.17 153.00 160.00  156
  3  \w    -84.00  -9.00   0.50    2.50    --  -48.17 120.00   1.00  150
  4  \w     49.00 113.00   0.50    2.50    --   48.17-153.00 119.00  128
  5  \w     31.00  93.00   0.50    2.50    --   48.17-120.00 -81.00  124
  6  \w   -163.00 -77.00   0.50   10.00    --  -91.75-120.00 -81.00  172
  7  \w    -84.00 -19.00   0.50   10.00    --  -91.75 120.00   1.00  130
  8  \w   -146.00 -54.00   0.50   10.00    --  -91.75-153.00 119.00  184
  9  \w     42.00 109.00   0.50   10.00    --  113.25-120.00 -81.00  134
 10  \w     76.00 164.00   0.50   10.00    --  113.25 153.00 160.00  176
 11  \w     98.00 178.00   0.50   10.00    --  113.25 120.00   1.00  160
 12  \w     49.00 132.00   0.50   10.00    --  113.25-153.00 119.00  166
 13  \w    -23.00  27.00   0.50    2.50    --  -48.17  19.00-180.00  100
 14  \w    -23.00  27.00   0.50    2.50    --  -48.17  19.00  90.00  100
 15  \w   -121.00 -73.00   0.50    2.50    --  -48.17-125.00 -60.00   96
 16  \w    -23.00  27.00   0.50    2.50    --  -48.17  19.00 -60.00  100
 17  \w    -23.00  27.00   0.50    2.50    --  -48.17  19.00-150.00  100
 18  \w    -23.00  27.00   0.50    2.50    --  -48.17  19.00 150.00  100
 19  \w    -26.00  23.00   0.50    2.50    --   48.17 -19.00 -90.00   98
 20  \w    -50.00 -20.00   0.50   10.00    --  -91.75  45.00  60.00   60
 21  \w    -50.00 -20.00   0.50   10.00    --  -91.75  45.00 150.00   60
 22  \w    -50.00 -20.00   0.50   10.00    --  -91.75  45.00  30.00   60
 23  \w     97.00 178.00   0.50   10.00    --  113.25  61.00 150.00  162
 24  \w     95.00 178.00   0.50   10.00    --  113.25 125.00  90.00  166
 25  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00 -90.00  128
 26  \w     95.00 178.00   0.50   10.00    --  113.25 125.00-150.00  166
 27  \w     42.00 107.00   0.50   10.00    --  113.25-103.00-165.50  130
 28  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00 120.00  128
 29  \w     42.00  72.00   0.50   10.00    --  113.25 -61.00 120.00   60
 30  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00 150.00  128
 31  \w     95.00 178.00   0.50   10.00    --  113.25 125.00  30.00  166
 32  \w     42.00 111.00   0.50   10.00    --  113.25-125.00  30.00  138
 33  \w    101.00 178.00   0.50   10.00    --  113.25  30.00 -30.00  154
 34  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00-150.00  128
 35  \w     42.00 111.00   0.50   10.00    --  113.25-125.00 120.00  138
 36  \w    101.00 178.00   0.50   10.00    --  113.25  45.00 -90.00  154
 37  \w     42.00 111.00   0.50   10.00    --  113.25-125.00-180.00  138
 38  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00  30.00  128
 39  \w    101.00 178.00   0.50   10.00    --  113.25  45.00  60.00  154
 40  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00 -30.00  128
 41  \w    100.00 178.00   0.50   10.00    --  113.25  15.00 -90.00  156
 42  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00-120.00  128
 43  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00 -60.00  128
 44  \w     91.00 178.00   0.50   10.00    --  113.25  77.00  60.00  174
 45  \w     42.00  72.00   0.50   10.00    --  113.25 -61.00   0.00   60
 46  \w    101.00 178.00   0.50   10.00    --  113.25  30.00  30.00  154
 47  \w     42.00  72.00   0.50   10.00    --  113.25 -61.00-180.00   60
 48  \w     42.00  72.00   0.50   10.00    --  113.25 -61.00 -90.00   60
 49  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00  60.00  128
 50  \w    101.00 178.00   0.50   10.00    --  113.25  45.00 120.00  154
 51  \w     42.00 106.00   0.50   10.00    --  113.25 -94.00-180.00  128
 52  \w     97.00 178.00   0.50   10.00    --  113.25  61.00  90.00  162
 53  \w   -121.00 -25.00   0.50    2.50    --  -48.17 -77.00 -30.00  192
 54  \w   -120.00 -33.00   0.50    2.50    --  -48.17 -57.00 120.00  174
 55  \w   -120.00 -33.00   0.50    2.50    --  -48.17 -57.00-120.00  174
 56  \w   -121.00 -25.00   0.50    2.50    --  -48.17 -77.00  60.00  192
;
_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      -0.0297523000
_diffrn_orient_matrix_UB_12      -0.0377300000
_diffrn_orient_matrix_UB_13      -0.0630235000
_diffrn_orient_matrix_UB_21      -0.0607706000
_diffrn_orient_matrix_UB_22      0.0317190000
_diffrn_orient_matrix_UB_23      -0.0701097000
_diffrn_orient_matrix_UB_31      0.1303460000
_diffrn_orient_matrix_UB_32      0.0061862000
_diffrn_orient_matrix_UB_33      -0.0249510000
_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  0.0877
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            132377
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.261
_diffrn_reflns_theta_min         2.850
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.159
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.216
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.55a (Rigaku Oxford Diffraction, 2022)
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            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       block
_exptl_crystal_F_000             2208
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.01
_exptl_crystal_size_rad          0.400
_refine_diff_density_max         0.982
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     605
_refine_ls_number_reflns         11380
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0573
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0928P)^2^+2.6513P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1440
_refine_ls_wR_factor_ref         0.1496
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9981
_reflns_number_total             11380
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01149c2.cif
_cod_data_source_block           CoL2b
_cod_depositor_comments
'Adding full bibliography for 7718951--7718957.cif.'
_cod_original_cell_volume        5246.25(8)
_cod_database_code               7718955
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 Cl4 Co2'
_chemical_oxdiff_usercomment
'C20 H20 N2 O2 Cl Co blue block 0.01 0.16 0.15   Rogers'
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.268
_olex2_refinement_description
;
There is a highly disordered methanol. The methanol was modelled as three separate 
methanols (O100-C100, O200-C200, O300-O300) disordered over three closely related 
positions behind PARTs instructions. 
Their occupancy was originally linked to free variable but was fixed at 0.5/0.25/0.25 
at later stages of the refinement. 
The minor components at 25% occupancy were refined isotropically. 
No hydrogens were located for these disordered solvents.

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. Others
 Fixed Sof: O100(0.5) C101(0.5) O200(0.25) C201(0.25) O300(0.25) C301(0.25)
3.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C4(H4A,H4B), C28(H28A,H28B), C14(H14A,H14B), C15(H15A,H15B),
 C40(H40A,H40B), C27(H27A,H27B), C16(H16A,H16B), C30(H30A,H30B), C2(H2A,H2B),
 C43(H43A,H43B), C41(H41A,H41B)
3.b Aromatic/amide H refined with riding coordinates:
 C22(H22), C48(H48), C19(H19), C33(H33), C35(H35), C20(H20), C32(H32),
 C46(H46), C45(H45), C6(H6), C7(H7), C9(H9)
3.c Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C25(H25A,H25B,H25C), C51(H51A,H51B,H51C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C), C52(H52A,H52B,H52C), C39(H39A,H39B,H39C), C50(H50A,
 H50B,H50C), C38(H38A,H38B,H38C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C),
 C11(H11A,H11B,H11C)
;
_shelx_res_checksum              47448
_shelx_hkl_checksum              48288
_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 2.488
_oxdiff_exptl_absorpt_empirical_full_min 0.427