Co(II) complexes of tetraazamacrocycles appended with amide or hydroxypropyl groups as paraCEST agents
Raymond, Jaclyn; Abozeid, Samira M.; Sokolow, Gregory Evan; Bond, Christopher J.; Yap, Constance E.; Nazarenko, Alexander Y.; Morrow, Janet; Dalton Transactions  (2023) –; doi:10.1039/D3DT01572F

data_7713237
_publ_section_title
;
 Co(II) complexes of tetraazamacrocycles appended with amide or
 hydroxypropyl groups as paraCEST agents
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01572F
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety
'2(C18 H38 Co N6 O4), 2(Cl4 Co), 2(H2 O), 2(C2 H3 N)'
_chemical_formula_sum            'C40 H86 Cl8 Co4 N14 O10'
_chemical_formula_weight         1442.54
_chemical_name_systematic
'(2,2'-[4,10-bis(2-hydroxypropyl)-1,4,7,10-tetraazadodecanane-1,7-diyl]diacetamide)cobalt(II) tetrachloridocobaltate monohydrate mono(acetonitrile) solvate'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dualspace
_atom_sites_solution_secondary   difmap
_audit_block_doi                 10.5517/ccdc.csd.cc25w83g
_audit_creation_date             2020-08-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-07 deposited with the CCDC.	2023-06-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.8813(8)
_cell_length_b                   18.4751(9)
_cell_length_c                   20.4087(10)
_cell_measurement_reflns_used    9198
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.71
_cell_measurement_theta_min      2.97
_cell_volume                     6365.1(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       ' APEX2 (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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      173
_diffrn_detector_area_resol_mean 10.4
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker PHOTON-100 CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0469
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            447993
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         32.678
_diffrn_reflns_theta_min         2.835
_diffrn_source                   sealedtube
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.419
_exptl_absorpt_correction_T_max  0.8313
_exptl_absorpt_correction_T_min  0.5458
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0675 before and 0.0624 after correction.
The Ratio of minimum to maximum transmission is 0.6566.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_description       block
_exptl_crystal_F_000             2992
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.59
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.15
_exptl_transmission_factor_max   1
_exptl_transmission_factor_min   0.67
_refine_diff_density_max         0.691
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Flack x determined using 8004 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     816
_refine_ls_number_reflns         23270
_refine_ls_number_restraints     504
_refine_ls_restrained_S_all      1.163
_refine_ls_R_factor_all          0.0505
_refine_ls_R_factor_gt           0.0352
_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^)+(0.0404P)^2^+2.8868P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0799
_refine_ls_wR_factor_ref         0.0882
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                19437
_reflns_number_total             23270
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01572f2.cif
_cod_data_source_block           mo_an040716_0m_a
_cod_database_code               7713237
_shelx_shelxl_version_number     2018/3
_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,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 H10A-N7
 2.1 with sigma of 0.02
 H4-C7
 3.7 with sigma of 0.02
 C32-C33 \\sim C25-C26 \\sim C38-C39 \\sim C30-C31 \\sim C29-C61 \\sim C36-C37
\\sim C34-C35 \\sim C27-C28
 with sigma of 0.01
 N11-C26 \\sim N11-C27 \\sim N11-C34 \\sim N11-C33 \\sim N14-C35 \\sim N14-C61
\\sim N14A-C36 \\sim N14A-
 C28 \\sim N13A-C37 \\sim N13A-C30 \\sim N13-C29 \\sim N13-C38 \\sim N12A-C31
\\sim N12A-C25 \\sim N12-C39
 \\sim N12-C32
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C33 \\sim C26 \\sim C32 \\sim C25 \\sim N12 \\sim N12A \\sim C45 \\sim C39
\\sim C31 \\sim C38 \\sim C30 \\sim N13 \\sim N13A \\sim C29 \\sim C37 \\sim
C61 \\sim C36 \\sim N14 \\sim N14A \\sim C35 \\sim C28 \\sim C34 \\sim C27
\\sim N11: within 1.9A with sigma of 0.01 and sigma for terminal atoms of 0.02
N9 \\sim C21 \\sim C22: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Uanis(C31) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Others
 Sof(H45C)=Sof(H45D)=Sof(H48C)=Sof(H48D)=Sof(N12A)=Sof(N13A)=Sof(N14A)=
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(C27)=Sof(H27A)=
 Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=
 Sof(H31A)=Sof(H31B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=
 Sof(C44)=Sof(H44A)=Sof(H44B)=1-FVAR(1)
 Sof(H45A)=Sof(H45B)=Sof(H48A)=Sof(H48B)=Sof(N12)=Sof(N13)=Sof(N14)=Sof(C29)=
 Sof(H29A)=Sof(H29B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C61)=
 Sof(H61A)=Sof(H61B)=FVAR(1)
5.a Free rotating group:
 O9(H9C,H9D), O10(H10A,H10B)
5.b Ternary CH refined with riding coordinates:
 C12(H12), C17(H17), C46(H46), C49(H49)
5.c Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5C,H5D), C6(H6C,H6D),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C14(H14A,H14B),
 C16(H16A,H16B), C40(H40A,H40B), C45(H45A,H45B), C45(H45C,H45D), C48(H48A,H48B),
  C48(H48C,H48D), C29(H29A,H29B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,
 H34B), C35(H35A,H35B), C38(H38A,H38B), C39(H39A,H39B), C42(H42A,H42B),
 C61(H61A,H61B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B),
  C30(H30A,H30B), C31(H31A,H31B), C36(H36A,H36B), C37(H37A,H37B), C44(H44A,H44B)
5.d X=CH2 refined with riding coordinates:
 N5(H5A,H5B), N6(H6A,H6B), N23(H23A,H23B), N24(H24A,H24B)
5.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C18(H18A,H18B,H18C), C47(H47A,H47B,H47C), C50(H50A,H50B,
 H50C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C)
5.f Idealised tetrahedral OH refined as rotating group:
 O8(H8)
;
_shelx_res_checksum              34313
_olex2_submission_special_instructions 'No special instructions were received'