Lanthanide complexes of DOTA-nitroxide conjugates for redox imaging: spectroelectrochemistry, CEST, relaxivity, and cytotoxicity.
Mouchel Dit Leguerrier, D.; Barré, R; Ruet, Q.; Imbert, D.; Philouze, C.; Fries, P. H.; Martel-Frachet, V; Molloy, J. K.; Thomas, F.; Dalton transactions (Cambridge, England : 2003) 50 (2021) 10826–10837; doi:10.1039/d1dt01628h

data_7707806
_publ_section_title
;
 Lanthanide complexes of DOTA-nitroxide conjugates for redox imaging:
 spectroelectrochemistry, CEST, relaxivity, and cytotoxicity.
;
_journal_issue                   31
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10826
_journal_page_last               10837
_journal_paper_doi               10.1039/d1dt01628h
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         '0.5(Br), C26 H47 N8 Na O4, H2 O, 0.5(Cl)'
_chemical_formula_sum            'C26 H49 Br0.5 Cl0.5 N8 Na O5'
_chemical_formula_weight         634.40
_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
_audit_creation_date             2020-04-14
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_audit_update_record
;
2020-04-15 deposited with the CCDC.	2021-06-25 downloaded from the CCDC.
;
_cell_angle_alpha                108.37(3)
_cell_angle_beta                 95.20(3)
_cell_angle_gamma                97.87(3)
_cell_formula_units_Z            2
_cell_length_a                   10.316(2)
_cell_length_b                   13.339(3)
_cell_length_c                   13.358(3)
_cell_measurement_reflns_used    26201
_cell_measurement_temperature    200
_cell_measurement_theta_max      25.000
_cell_measurement_theta_min      1.623
_cell_volume                     1710.4(7)
_computing_cell_refinement       EvalCCD
_computing_data_collection       Collect
_computing_data_reduction        EvalCCD
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_diffrn_ambient_temperature      200
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'APEX II'
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       '\k-geometry 4 circles diffractometer'
_diffrn_measurement_device_type  'Bruker-AXS-enraf-nonius KappaAPEXII'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    'Montel optic'
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0744
_diffrn_reflns_av_unetI/netI     0.0518
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            26201
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.623
_diffrn_source                   'Incoatec ISG250'
_diffrn_source_target            Mo
_diffrn_source_type              'Microfocus sealed tube'
_exptl_absorpt_coefficient_mu    0.714
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.530420
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2004/1 (Bruker,2004) was used for absorption correction.
R(int) was 0.2997 before and 0.1064 after correction.
The Ratio of minimum to maximum transmission is 0.5304.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.232
_exptl_crystal_description       block
_exptl_crystal_F_000             676
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.643
_refine_diff_density_min         -0.328
_refine_diff_density_rms         0.075
_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     635
_refine_ls_number_reflns         5952
_refine_ls_number_restraints     1068
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0962
_refine_ls_R_factor_gt           0.0741
_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^)+(0.1115P)^2^+1.6066P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1995
_refine_ls_wR_factor_ref         0.2201
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4646
_reflns_number_total             5952
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01628h2.cif
_cod_data_source_block           sad2
_cod_depositor_comments          'Adding full bibliography for 7707806.cif.'
_cod_original_formula_sum        'C26 H49 Br0.50 Cl0.50 N8 Na O5'
_cod_database_code               7707806
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups,
  All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C1-C2B
 1.5 with sigma of 0.02
 C2B-C3B
 1.1 with sigma of 0.02
 C26B-C21B
 1.5 with sigma of 0.02
 C25B-C21B
 1.5 with sigma of 0.02
3. Rigid bond restraints
 C3B, Na1, O2, O1, O3, N3A, N1B, N2A, N1A, C13, N4B, N4A, N2B, N3B, C15, C17,
 C14A, C8A, C7A, C16A, C10A, C9A, C12, C6A, C5A, C1A, C11A, C4A, N6, C10B, C16B,
  C9B, C4B, C1, C11B, C6B, C5B, C8B, C7B, C14B, N7, N8, C2A, H6A, H6B, C2B, C18,
  H8A, H8B, C3A, C19A, C22A, C19B, C22B, C20A, C21A, C20B, C21B, N5, C23A, C24A,
  C26A, C25A, C23B, C24B, C25B, C26B, O4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl1B, Cl1C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C3B \\sim Na1 \\sim O2 \\sim O1 \\sim O3 \\sim N3A \\sim N4A \\sim N2A \\sim
N1A \\sim C13 \\sim N4B \\sim N1B \\sim N2B \\sim N3B \\sim C15 \\sim C17 \\sim
C14A \\sim C8A \\sim C7A \\sim C16A \\sim C10A \\sim C9A \\sim C12 \\sim C6A
\\sim C5A \\sim C1A \\sim C11A \\sim C4A \\sim N6 \\sim C10B \\sim C16B \\sim
C9B \\sim C4B \\sim C1 \\sim C11B \\sim C6B \\sim C5B \\sim C8B \\sim C7B \\sim
C14B \\sim N7 \\sim N8 \\sim C2A \\sim H6A \\sim H6B \\sim C2B \\sim C18 \\sim
H8A \\sim H8B \\sim C3A \\sim C19A \\sim C22A \\sim C19B \\sim C22B \\sim C20A
\\sim C21A \\sim C20B \\sim C21B \\sim N5 \\sim C23A \\sim C24A \\sim C26A
\\sim C25A \\sim C23B \\sim C24B \\sim C25B \\sim C26B \\sim O4: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
Cl1B \\sim Cl1C: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Cl1A \\sim Cl1B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
Cl1A \\sim Cl1B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
5. Others
 Sof(H18A)=Sof(H12C)=Sof(H12D)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(C6B)=Sof(H6BA)=
 Sof(H6BB)=Sof(C10B)=Sof(H10C)=Sof(H10D)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(N4B)=
 Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(N1B)=Sof(C16B)=Sof(H16C)=Sof(H16D)=Sof(C7B)=
 Sof(H7BA)=Sof(H7BB)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(N2B)=Sof(C21B)=Sof(C25B)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C20B)=Sof(C23B)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C19B)=Sof(H19C)=Sof(H19D)=Sof(C24B)=
 Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C14B)=Sof(H14C)=Sof(H14D)=Sof(C22B)=
 Sof(H22C)=Sof(H22D)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(N3B)=Sof(C11B)=
 Sof(H11C)=Sof(H11D)=Sof(C3B)=Sof(H3B)=Sof(C2B)=1-FVAR(1)
 Sof(N3A)=Sof(N4A)=Sof(N2A)=Sof(N1A)=Sof(C14A)=Sof(H14A)=Sof(H14B)=Sof(H18)=
 Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(C21A)=Sof(C19A)=Sof(H19A)=Sof(H19B)=
 Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(C20A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H12A)=
 Sof(H12B)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C25A)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C23A)=
 Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(C11A)=
 Sof(H11A)=Sof(H11B)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C4A)=Sof(H4AA)=
 Sof(H4AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C2A)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=
 Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C3A)=Sof(H3A)=FVAR(1)
 Sof(Cl1B)=0.4*(1-FVAR(3))
 Sof(Cl1A)=0.4*FVAR(3)
 Fixed Sof: Br1(0.5) Cl1C(0.1)
6.a Free rotating group:
 O5(H5A,H5B)
6.b Ternary CH refined with riding coordinates:
 C18(H18), C18(H18A)
6.c Secondary CH2 refined with riding coordinates:
 C14A(H14A,H14B), C16A(H16A,H16B), C19A(H19A,H19B), C22A(H22A,H22B), C8A(H8AA,
 H8AB), C12(H12A,H12B), C12(H12C,H12D), C6A(H6AA,H6AB), C1A(H1AA,H1AB),
 C10A(H10A,H10B), C11A(H11A,H11B), C4A(H4AA,H4AB), C9A(H9AA,H9AB), C5A(H5AA,
 H5AB), C7A(H7AA,H7AB), C8B(H8BA,H8BB), C6B(H6BA,H6BB), C10B(H10C,H10D),
 C4B(H4BA,H4BB), C5B(H5BA,H5BB), C16B(H16C,H16D), C7B(H7BA,H7BB), C9B(H9BA,
 H9BB), C1(H1A,H1B), C19B(H19C,H19D), C14B(H14C,H14D), C22B(H22C,H22D),
 C11B(H11C,H11D)
6.d Aromatic/amide H refined with riding coordinates:
 N7(H7)
6.e X=CH2 refined with riding coordinates:
 N8(H8A,H8B), N6(H6A,H6B)
6.f Idealised Me refined as rotating group:
 C26A(H26A,H26B,H26C), C25A(H25A,H25B,H25C), C23A(H23A,H23B,H23C), C24A(H24A,
 H24B,H24C), C25B(H25D,H25E,H25F), C23B(H23D,H23E,H23F), C24B(H24D,H24E,H24F),
 C26B(H26D,H26E,H26F)
6.g :
 C3A(H3A), C3B(H3B)
;
_shelx_res_checksum              63687
_shelx_hkl_checksum              77760
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'