Fluorinated EuII-based multimodal contrast agent for temperature- and redox-responsive magnetic resonance imaging
Basal, Lina A.; Bailey, Matthew D.; Romero, Jonathan; Ali, Meser M.; Kurenbekova, Lyazat; Yustein, Jason; Pautler, Robia G.; Allen, Matthew J.; Chem. Sci.  (2017) –; doi:10.1039/C7SC03142D

data_1547803
_publ_section_title
;
 Fluorinated EuII-based multimodal contrast agent for temperature- and
 redox-responsive magnetic resonance imaging
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC03142D
_journal_year                    2017
_chemical_formula_moiety
'C44.5 H52 Eu F8.5 N8 O5, 3(Cl), 5(H2 O), O, 0.5(C7 H4 F3), 2(F)'
_chemical_formula_sum            'C48 H64 Cl3 Eu F12 N8 O11'
_chemical_formula_weight         1415.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_symmetry_space_group_name_Hall  '-P 2yac'
_symmetry_space_group_name_H-M   'P 1 2/n 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-10-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-10-04 deposited with the CCDC.
2017-10-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.775(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.8737(14)
_cell_length_b                   26.268(4)
_cell_length_c                   11.6670(14)
_cell_measurement_reflns_used    9984
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      20.94
_cell_measurement_theta_min      2.27
_cell_volume                     2948.5(7)
_computing_cell_refinement       'SAINT V8.18C (?, 2016)'
_computing_data_reduction        'SAINT V8.18C (?, 2016)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.1
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0819
_diffrn_reflns_av_unetI/netI     0.0418
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            129335
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.481
_diffrn_reflns_theta_min         1.550
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.300
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6779
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0823 before and 0.0695 after correction.
The Ratio of minimum to maximum transmission is 0.9091.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.594
_exptl_crystal_description       flakes
_exptl_crystal_F_000             1436
_exptl_crystal_size_max          0.426
_exptl_crystal_size_mid          0.256
_exptl_crystal_size_min          0.207
_refine_diff_density_max         3.220
_refine_diff_density_min         -2.573
_refine_diff_density_rms         0.210
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     833
_refine_ls_number_reflns         6841
_refine_ls_number_restraints     230
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0767
_refine_ls_R_factor_gt           0.0671
_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^)+49.0979P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1480
_refine_ls_wR_factor_ref         0.1534
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6202
_reflns_number_total             6841
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03142d2.cif
_cod_data_source_block           2EuIII
_cod_database_code               1547803
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.775
_shelx_estimated_absorpt_t_min   0.607
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9702(11)
 0.0298(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H,H) groups
3. Restrained distances
 C47-F11 = C47-F12 = C47-F10
 1.328 with sigma of 0.02
 C47-F14A = C47-F8A = C47-F4AB
 1.328 with sigma of 0.02
 F11-F12 = F11-F10 = F12-F10
 2.125 with sigma of 0.02
 C23-F6 = C23-F5 = C23-F4
 1.328 with sigma of 0.02
 F4-F5 = F4-F6 = F5-F6
 2.125 with sigma of 0.02
 C48-F9 = C48-F7 = C48-F8
 1.328 with sigma of 0.02
 F9-F7 = F9-F8 = F7-F8
 2.125 with sigma of 0.02
 C55-F19 = C55-F21 = C55-F20
 1.328 with sigma of 0.02
 F19-F21 = F19-F20 = F21-F20
 2.125 with sigma of 0.02
 F4AB-F14A = F4AB-F8A = F14A-F8A
 2.125 with sigma of 0.02
 F4A-F6A = F4A-F21A = F6A-F21A
 2.125 with sigma of 0.02
4. Restrained planarity
 C48, C44, C45, C46, C41, C42, C43, C34
 with sigma of 0.1
 C55, C52, C53, C54, C49, C50, C51
 with sigma of 0.1
5. Rigid bond restraints
 C23, F6, C23, F5, C23, F4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C47, F11, C47, F12, C47, F10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C12, C13, C45, C46, C34, C41, C43, C42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N1, C29, C30, C29
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
N2 \\sim C31: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C49) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C42)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(F8A) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F14A)
\\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F6A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C12) = Uanis(C11)
7. Rigid body (RIGU) restrains
 C23, F6, C23, F5, C23, F4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, F21A, C23, F4A, C23, F6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, F11, C47, F12, C47, F10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, F14A, C47, F4AB, C47, F8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C48, F9, C48, F7, C48, F8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C55, F19, C55, F21, C55, F20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24, F2, C24, F3, C24, F1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8. Others
 Sof(C5)=Sof(H5A)=Sof(H5B)=1-FVAR(1)
 Sof(C29)=Sof(H29A)=Sof(H29B)=FVAR(1)
 Fixed Sof: H3A(0.5) H3B(0.5) H8A(0.5) H8B(0.5) C25(0.5) H25A(0.5) H25B(0.5)
 O4(0.5) C4(0.5) H4A(0.5) H4B(0.5) C27(0.5) H27A(0.5) H27B(0.5) O2(0.5) C2(0.5)
 H2A(0.5) H2B(0.5) O5(0.5) C22(0.5) H22(0.5) N6(0.5) H6(0.5) N4(0.5) H4(0.5)
 O1(0.5) N5(0.5) H5(0.5) C7(0.5) H7A(0.5) H7B(0.5) C11(0.5) N3(0.5) H3(0.5)
 C30(0.5) C32(0.5) C13(0.5) H13(0.5) C6(0.5) C16(0.5) H16(0.5) C8(0.5) C35(0.5)
 C34(0.5) H34A(0.5) H34B(0.5) C10(0.5) H10A(0.5) H10B(0.5) C17(0.5) C9(0.5)
 H9A(0.5) H9B(0.5) C33(0.5) H33A(0.5) H33B(0.5) C21(0.5) H21(0.5) C19(0.5)
 H19(0.5) C14(0.5) C12(0.5) H12(0.5) C36(0.5) H36(0.5) C18(0.5) H18(0.5)
 C15(0.5) H15(0.5) C37(0.5) H37(0.5) C39(0.5) H39(0.5) C40(0.5) H40(0.5)
 C42(0.25) H42(0.25) C54(0.25) H54(0.25) C41(0.25) F9(0.25) C48(0.25) F7(0.25)
 F8(0.25) F1(0.5) C24(0.5) C38(0.5) F3(0.5) C23(0.5) F5(0.25) F4(0.25) F6(0.25)
 C20(0.5) C31(0.5) H31A(0.5) H31B(0.5) C28(0.5) H28A(0.5) H28B(0.5) C3(0.5)
 H3C(0.5) H3D(0.5) C26(0.5) H26A(0.5) H26B(0.5) C1(0.5) H1A(0.5) H1B(0.5)
 C47(0.5) F11(0.25) C43(0.25) H43(0.25) C51(0.25) H51(0.25) C52(0.25) C44(0.25)
 C45(0.25) H45(0.25) C53(0.25) H53(0.25) C46(0.25) H46(0.25) C50(0.25)
 H50(0.25) C49(0.25) F20(0.25) F21(0.25) C55(0.25) F19(0.25) F12(0.25)
 F10(0.25) F4AB(0.25) F8A(0.25) F14A(0.25) F21A(0.25) F6A(0.25) F4A(0.25)
 F2(0.5)
9.a Free rotating group:
 O9(H9C,H9D), O8(H8A,H8B), O7(H7C,H7D)
9.b Rotating group:
 O3(H3A,H3B)
9.c Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C4(H4A,H4B), C27(H27A,H27B), C2(H2A,H2B), C7(H7A,H7B),
 C29(H29A,H29B), C34(H34A,H34B), C10(H10A,H10B), C9(H9A,H9B), C33(H33A,H33B),
 C31(H31A,H31B), C5(H5A,H5B), C28(H28A,H28B), C3(H3C,H3D), C26(H26A,H26B),
 C1(H1A,H1B)
9.d Aromatic/amide H refined with riding coordinates:
 C22(H22), N6(H6), N4(H4), N5(H5), N3(H3), C13(H13), C16(H16), C21(H21),
 C19(H19), C12(H12), C36(H36), C18(H18), C15(H15), C37(H37), C39(H39), C40(H40),
  C42(H42), C54(H54), C43(H43), C51(H51), C45(H45), C53(H53), C46(H46), C50(H50)
;
_shelx_res_checksum              12521
_olex2_submission_special_instructions 'No special instructions were received'