Macrocyclic complexes of Fe(III) with mixed hydroxypropyl and phenolate or amide pendants as T<sub>1</sub> MRI probes.
Kras, Elizabeth A.; Cineus, Roy; Crawley, Matthew R.; Morrow, Janet R.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 4154–4164; doi:10.1039/d3dt04013e

data_7715086
_publ_section_title
;
 Macrocyclic complexes of Fe(III) with mixed hydroxypropyl and phenolate
 or amide pendants as T<sub>1</sub> MRI probes.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4154
_journal_page_last               4164
_journal_paper_doi               10.1039/d3dt04013e
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety
'1.503(Br), C19 H32 Fe N3 O3, 0.497(Cl), 1.75[C2H3N]'
_chemical_formula_sum            'C22.5 H37.25 Br1.5 Cl0.5 Fe N4.75 O3'
_chemical_formula_weight         615.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-08
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-01-09 deposited with the CCDC.	2024-01-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.804(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.8951(5)
_cell_length_b                   6.9779(2)
_cell_length_c                   15.6193(6)
_cell_measurement_reflns_used    5377
_cell_measurement_temperature    100.00(13)
_cell_measurement_theta_max      77.3600
_cell_measurement_theta_min      2.8510
_cell_volume                     1392.42(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.92a 64-bit (release 05-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.983
_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   -120.00 -27.00   0.50    2.00    --  -47.65  -7.00  25.00  186
  2  \w    -29.00  26.00   0.50    2.00    --  -47.65   7.00-159.00  110
  3  \w     66.00 118.00   0.50    2.00    --   47.65   7.00-159.00  104
  4  \w   -143.00-116.00   0.50    8.00    --  -91.75  -7.00  25.00   54
  5  \w    147.00 172.00   0.50    8.00    --  113.25   7.00-159.00   50
  6  \w     87.00 119.00   0.50    8.00    --  113.25   7.00-159.00   64
  7  \w     46.00  75.00   0.50    2.00    --   47.65 -99.00  30.00   58
  8  \w    -18.00  42.00   0.50    2.00    --   47.65 -38.00 -90.00  120
  9  \w     52.00  93.00   0.50    2.00    --   47.65-125.00-180.00   82
 10  \w    -23.00   2.00   0.50    2.00    --   47.65  -7.00  25.00   50
 11  \w    103.00 178.00   0.50    8.00    --  113.25  30.00  90.00  150
 12  \w     52.00  78.00   0.50    8.00    --  113.25 -77.00 -60.00   52
 13  \w     61.00 106.00   0.50    8.00    --  113.25 -95.00 -60.00   90
 14  \w    121.00 153.00   0.50    8.00    --  113.25  45.00  30.00   64
 15  \w     66.00  95.00   0.50    8.00    --  113.25 -95.00   0.00   58
 16  \w    102.00 141.00   0.50    8.00    --  113.25  61.00-180.00   78
 17  \w    108.00 135.00   0.50    8.00    --  113.25  45.00 -90.00   54
 18  \w    143.00 178.00   0.50    8.00    --  113.25  45.00 -90.00   70
 19  \w     44.00  85.00   0.50    8.00    --  113.25 -77.00 120.00   82
 20  \w     43.00  94.00   0.50    8.00    --  113.25 -77.00-120.00  102
 21  \w     42.00  70.00   0.50    8.00    --  113.25 -61.00-180.00   56
 22  \w     44.00  95.00   0.50    8.00    --  113.25 -95.00 120.00  102
 23  \w    144.00 177.00   0.50    8.00    --  113.25  45.00 150.00   66
 24  \w     62.00 100.00   0.50    8.00    --  113.25 -77.00-180.00   76
 25  \w     81.00 110.00   0.50    8.00    --  113.25-125.00 -60.00   58
 26  \w     97.00 123.00   0.50    8.00    --  113.25  77.00 150.00   52
 27  \w    104.00 137.00   0.50    8.00    --  113.25  45.00 150.00   66
 28  \w     42.00  67.00   0.50    8.00    --  113.25 -61.00 -90.00   50
 29  \w     70.00 103.00   0.50    8.00    --  113.25 -95.00  90.00   66
 30  \w    121.00 155.00   0.50    8.00    --  113.25  45.00-120.00   68
 31  \w    109.00 178.00   0.50    8.00    --  113.25  61.00-150.00  138
 32  \w     42.00  75.00   0.50    8.00    --  113.25 -77.00 -30.00   66
 33  \w     85.00 110.00   0.50    8.00    --  113.25-125.00 -90.00   50
 34  \w     75.00 101.00   0.50    8.00    --  113.25 -95.00 -30.00   52
 35  \w     43.00  74.00   0.50    8.00    --  113.25 -95.00  30.00   62
 36  \w     59.00 103.00   0.50    8.00    --  113.25-125.00   0.00   88
 37  \w     43.00  70.00   0.50    8.00    --  113.25 -61.00  60.00   54
 38  \w     46.00  71.00   0.50    8.00    --  113.25 -95.00  60.00   50
;
_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      0.0737691000
_diffrn_orient_matrix_UB_12      0.0086037000
_diffrn_orient_matrix_UB_13      -0.0697161000
_diffrn_orient_matrix_UB_21      -0.0946569000
_diffrn_orient_matrix_UB_22      -0.0209109000
_diffrn_orient_matrix_UB_23      -0.0709723000
_diffrn_orient_matrix_UB_31      -0.0117930000
_diffrn_orient_matrix_UB_32      0.2195719000
_diffrn_orient_matrix_UB_33      -0.0039492000
_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  0.0550
_diffrn_reflns_av_unetI/netI     0.0510
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            12511
_diffrn_reflns_point_group_measured_fraction_full 0.761
_diffrn_reflns_point_group_measured_fraction_max 0.731
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.768
_diffrn_reflns_theta_min         2.856
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.558
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.396
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
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            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.469
_exptl_crystal_description       needle
_exptl_crystal_F_000             633
_exptl_crystal_size_max          0.303
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.378
_refine_diff_density_min         -0.581
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 814 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     259
_refine_ls_number_reflns         4430
_refine_ls_number_restraints     268
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0452
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0787P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1213
_refine_ls_wR_factor_ref         0.1282
_reflns_Friedel_coverage         0.372
_reflns_Friedel_fraction_full    0.479
_reflns_Friedel_fraction_max     0.433
_reflns_number_gt                3569
_reflns_number_total             4430
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt04013e2.cif
_cod_data_source_block           fe_phenol_tob_2_final
_cod_depositor_comments          'Adding full bibliography for 7715086.cif.'
_cod_original_formula_sum        'C22.50 H37.25 Br1.50 Cl0.50 Fe N4.75 O3'
_cod_database_code               7715086
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'FeC22.6N4.8O3Br2H37.4 '
_shelx_estimated_absorpt_t_max   0.864
_shelx_estimated_absorpt_t_min   0.208
_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, All O(H) groups
2. Shared sites
{Br1, Cl1}
{Br2, Cl2}
3. 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
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(Br1) = Uanis(Cl1)
Uanis(Br2) = Uanis(Cl2)
5. Others
 Sof(Cl1)=1-FVAR(1)
 Sof(Br1)=FVAR(1)
 Sof(Cl2)=1-FVAR(2)
 Sof(Br2)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C15(H15), C18(H18)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C7(H7A,H7B), C2(H2A,H2B), C14(H14A,H14B), C17(H17A,H17B), C4(H4A,
 H4B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B)
6.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C9(H9), C11(H11), C10(H10)
6.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C16(H16A,H16B,H16C)
6.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O3(H3)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              66798
_shelx_hkl_checksum              12492
_shelx_fab_checksum              61846
_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 2.473
_oxdiff_exptl_absorpt_empirical_full_min 0.634