Seven-Coordinate Co(II), Fe(II) and Six-Coordinate Ni(II) Amide-Appended Macrocyclic Complexes as ParaCEST Agents in Biological Media.
Olatunde, Abiola O.; Cox, Jordan M.; Daddario, Michael D.; Spernyak, Joseph A.; Benedict, Jason B.; Morrow, Janet R.; Inorganic chemistry 53 (2014) 8311–8321; doi:10.1021/ic5006083

data_4338414
_publ_section_title
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 Seven-Coordinate Co(II), Fe(II) and Six-Coordinate Ni(II) Amide-Appended
 Macrocyclic Complexes as ParaCEST Agents in Biological Media.
;
_journal_issue                   16
_journal_name_full               'Inorganic chemistry'
_journal_page_first              8311
_journal_page_last               8321
_journal_paper_doi               10.1021/ic5006083
_journal_volume                  53
_journal_year                    2014
_chemical_formula_moiety
'C14 H28 N4 Ni O5, C F3 O3 S, 0.88(C1.01 F3.02 O3 S), H2 O, 0.11(C F3 O3.18 S1.06)'
_chemical_formula_sum            'C16 H30 F6 N4 Ni O12 S2'
_chemical_formula_weight         707.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_cell_angle_alpha                90
_cell_angle_beta                 95.4010(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.6016(6)
_cell_length_b                   23.6949(11)
_cell_length_c                   20.8143(10)
_cell_measurement_temperature    90
_cell_volume                     5696.4(5)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      90
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX2 microfocus rotating anode'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0727
_diffrn_reflns_av_unetI/netI     0.0438
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            68719
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         31.153
_diffrn_reflns_theta_min         1.719
_diffrn_source                   'microfocus rotating anode'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    0.929
_exptl_absorpt_correction_T_max  0.7462
_exptl_absorpt_correction_T_min  0.6647
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0758 before and 0.0637 after correction.
The Ratio of minimum to maximum transmission is 0.8908.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.649
_exptl_crystal_description       plate
_exptl_crystal_F_000             2912
_exptl_crystal_preparation
'L was prepared using a previously reported procedure.7 Metal salts were complexed to L in equimolar ratio in either ethanol (CoII), or acetonitrile (NiII), stirred at room temp for over 1 hour and isolated as previously reported.7,10 Fe(CF3SO3)2 and L were added under argon to prevent the oxidation of the free FeII to FeIII in solution. [Fe(L)]2+ was isolated as a slightly yellowish tan powder.'
_exptl_crystal_recrystallization_method
'grown over several days by vapor diffusion of hexane into acetonitrile'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.824
_refine_diff_density_min         -0.475
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     404
_refine_ls_number_reflns         9148
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0371
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0511P)^2^+2.9407P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0884
_refine_ls_wR_factor_ref         0.0976
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7107
_reflns_number_total             9148
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5006083_si_002.cif
_cod_data_source_block           ni(l)
_cod_depositor_comments
'Adding full bibliography for 4338412--4338414.cif.'
_cod_database_code               4338414
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
2. Restrained distances
 H12A-O12 = O12-H12B
 0.85 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F4) = Uanis(F4A)
Uanis(F5) = Uanis(F5A)
Uanis(F6) = Uanis(F6A)
Uanis(C16) = Uanis(C16A)
Uanis(O10) = Uanis(O10A)
Uanis(O11) = Uanis(O11A)
Uanis(O9) = Uanis(O9A)
Uanis(S2) = Uanis(S2A)
4. Others
 Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(C16A)=1-FVAR(1)
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(C16)=FVAR(1)
 Sof(O10A)=Sof(O11A)=Sof(O9A)=Sof(S2A)=1-FVAR(2)
 Sof(S2)=Sof(O10)=Sof(O11)=Sof(O9)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C8(H8A,H8B), C10(H10A,H10B), C3(H3C,H3D), C7(H7A,H7B), C4(H4C,
 H4D), C2(H2A,H2B), C5(H5A,H5B), C11(H11A,H11B), C1(H1A,H1B), C6(H6A,H6B),
 C9(H9A,H9B)
5.b X=CH2 refined with riding coordinates:
 N4(H4A,H4B), N3(H3A,H3B)
;
_shelx_res_checksum              49946
_shelx_hkl_checksum              5538
_olex2_computing_structure_refinement_long 'ShelXL (Sheldrick, 2008)'