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_7713234
_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(C20 H44 Co N4 O4), 2(Cl), Cl4 Co, 1.69(H2 O), C2 H3 N'
_chemical_formula_sum            'C42 H94.38 Cl6 Co3 N9 O9.69'
_chemical_formula_weight         1270.39
_chemical_name_systematic
'1,1',1'',1'''-(1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetrakis-(propan-2-ol)cobalt(II) dichloride 1,1',1'',1'''-(1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetrakis-(propan-2-ol)cobalt(II)tetrachloridocobaltate dihydrate monoacetonitrile solvate'
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dualspace
_atom_sites_solution_secondary   difmap
_audit_block_doi                 10.5517/ccdc.csd.cc25w81d
_audit_creation_date             2020-07-29
_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                76.878(2)
_cell_angle_beta                 78.518(2)
_cell_angle_gamma                89.593(2)
_cell_formula_units_Z            1
_cell_length_a                   9.3476(7)
_cell_length_b                   10.4026(7)
_cell_length_c                   15.7740(11)
_cell_measurement_reflns_used    9892
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      22.18
_cell_measurement_theta_min      2.83
_cell_volume                     1462.74(18)
_computing_cell_refinement       'SAINT v8.34A (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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 10.4
_diffrn_measured_fraction_theta_full 0.996
_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  0.0700
_diffrn_reflns_av_unetI/netI     0.0649
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            68318
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        25.729
_diffrn_reflns_theta_max         25.729
_diffrn_reflns_theta_min         2.830
_diffrn_source                   sealedtube
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.171
_exptl_absorpt_correction_T_max  0.9502
_exptl_absorpt_correction_T_min  0.7687
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0556 before and 0.0494 after correction.
The Ratio of minimum to maximum transmission is 0.8090.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            blue
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_description       block
_exptl_crystal_F_000             670
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.07
_exptl_transmission_factor_max   1
_exptl_transmission_factor_min   0.81
_refine_diff_density_max         0.433
_refine_diff_density_min         -0.605
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 3558 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.001(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     704
_refine_ls_number_reflns         10954
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0750
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0255P)^2^+0.8912P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0634
_refine_ls_wR_factor_ref         0.0719
_reflns_Friedel_coverage         0.968
_reflns_Friedel_fraction_full    0.964
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                8409
_reflns_number_total             10954
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01572f2.cif
_cod_data_source_block           mo_jm101716_0m
_cod_database_code               7713234
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O3-H3
 0.85 with sigma of 0.02
 O5-H5
 0.85 with sigma of 0.02
 O1-H1
 0.85 with sigma of 0.02
 O7-H7
 0.85 with sigma of 0.02
 O6-H6
 0.85 with sigma of 0.02
 O2-H2
 0.85 with sigma of 0.02
 H10B-O9
 2 with sigma of 0.02
3. Others
 Sof(Co4)=Sof(Cl7)=Sof(Cl8)=Sof(Cl9)=1-FVAR(1)
 Sof(Co3)=Sof(Cl3)=Sof(Cl4)=Sof(Cl6)=FVAR(1)
 Sof(O10)=Sof(H10A)=Sof(H10B)=FVAR(2)
4.a Free rotating group:
 O9(H9C,H9D), O10(H10A,H10B)
4.b Ternary CH refined with riding coordinates:
 C10(H10), C13(H13), C16(H16), C19(H19), C30(H30), C33(H33), C36(H36), C39(H39)
4.c Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C12(H12A,H12B), C15(H15A,H15B),
 C18(H18A,H18B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B),
  C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,
 H29B), C32(H32A,H32B), C35(H35A,H35B), C38(H38A,H38B)
4.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C), C20(H20A,H20B,
 H20C), C31(H31A,H31B,H31C), C34(H34A,H34B,H34C), C37(H37A,H37B,H37C), C40(H40A,
 H40B,H40C), C42(H42A,H42B,H42C)
4.e Idealised tetrahedral OH refined as rotating group:
 O4(H4), O8(H8)
;
_shelx_res_checksum              44655
_olex2_submission_special_instructions 'No special instructions were received'