Di- and tri-valent metal complexes with tris-amide-functionalised 1,4,7-triazacyclononane chelators
O’Callaghan, Charley; Greenacre, Victoria K.; Reid, Gillian; New Journal of Chemistry 49 (2025) 4061–4071; doi:10.1039/D4NJ05327C

data_7063643
_publ_section_title
;
 Di- and tri-valent metal complexes with tris-amide-functionalised
 1,4,7-triazacyclononane chelators
;
_journal_issue                   10
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              4061
_journal_page_last               4071
_journal_paper_doi               10.1039/D4NJ05327C
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C24 H48 N6 Ni O3, 2(N O3), 0.249(H2 O)'
_chemical_formula_sum            'C24 H48.498 N8 Ni O9.249'
_chemical_formula_weight         655.892
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_Int_Tables_number      14
_audit_creation_date             2025-02-03
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.01.22 svn.rc7346086 for OlexSys, GUI svn.r7128)
;
_audit_update_record
;
2025-02-04 deposited with the CCDC.	2025-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 119.134(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.7391(7)
_cell_length_b                   11.5230(4)
_cell_length_c                   18.2239(7)
_cell_measurement_reflns_used    21698
_cell_measurement_temperature    99.9(2)
_cell_measurement_theta_max      31.3110
_cell_measurement_theta_min      3.7400
_cell_volume                     3253.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9975
_diffrn_measured_fraction_theta_max 0.9982
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     22.00  64.00   0.50    2.00    --  -18.58  19.00-120.00   84
  2  \w    -42.00  59.00   0.50    2.00    --  -18.58  57.00 -30.00  202
  3  \w    -42.00  59.00   0.50    2.00    --  -18.58  57.00  30.00  202
  4  \w     22.00  64.00   0.50    2.00    --  -18.58  19.00 150.00   84
  5  \w     22.00  64.00   0.50    2.00    --  -18.58  19.00 -90.00   84
  6  \w     22.00  64.00   0.50    2.00    --  -18.58  19.00 -60.00   84
  7  \w    -56.00   9.00   0.50    2.00    --  -18.58 -57.00-150.00  130
  8  \w    -25.00   3.00   0.50    2.00    --   21.24 104.00 144.66   56
  9  \w    -56.00  48.00   0.50    2.00    --   21.24 -57.00  30.00  208
 10  \w      0.00  65.00   0.50    2.00    --   21.24 -99.00-150.00  130
 11  \w    -39.00 -13.00   0.50    2.00    --   21.24 129.00  35.39   52
 12  \w    -18.00  54.00   0.50    2.00    --   21.24 -77.00 150.00  144
 13  \w    -56.00   9.00   0.50    2.00    --  -18.58 -57.00 120.00  130
 14  \w   -102.00 -67.00   0.50    2.00    --  -18.58 -38.00-180.00   70
 15  \w     22.00  64.00   0.50    2.00    --  -18.58  19.00 120.00   84
 16  \w   -102.00   9.00   0.50    2.00    --  -18.58 -38.00   0.00  222
 17  \w    -56.00   9.00   0.50    2.00    --  -18.58 -57.00 -60.00  130
 18  \w      0.00  65.00   0.50    2.00    --   21.24 -99.00 -90.00  130
 19  \w    -35.00  -9.00   0.50    2.00    --   21.24 122.00  93.76   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0647
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 0.9975
_diffrn_reflns_Laue_measured_fraction_max 0.9982
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            81694
_diffrn_reflns_point_group_measured_fraction_full 0.9975
_diffrn_reflns_point_group_measured_fraction_max 0.9982
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         28.70
_diffrn_reflns_theta_min         3.50
_exptl_absorpt_coefficient_mu    0.656
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90623
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'intense purple'
_exptl_crystal_density_diffrn    1.339
_exptl_crystal_description       block
_exptl_crystal_F_000             1404.471
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.7613
_refine_diff_density_min         -1.0319
_refine_diff_density_rms         0.0983
_refine_ls_d_res_high            0.7400
_refine_ls_d_res_low             5.8134
_refine_ls_goodness_of_fit_ref   1.0326
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    115
_refine_ls_number_parameters     497
_refine_ls_number_reflns         8412
_refine_ls_number_restraints     350
_refine_ls_restrained_S_all      1.0075
_refine_ls_R_factor_all          0.0827
_refine_ls_R_factor_gt           0.0556
_refine_ls_shift/su_max          0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0466P)^2^+4.1981P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1245
_refine_ls_wR_factor_ref         0.1368
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              12
_reflns_limit_h_min              -23
_reflns_limit_k_max              15
_reflns_limit_k_min              0
_reflns_limit_l_max              24
_reflns_limit_l_min              -11
_reflns_number_gt                6122
_reflns_number_total             8412
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4nj05327c2.cif
_cod_data_source_block           2021dept_gr_cb_co(lb)_auto_reprocessed_2
_cod_depositor_comments
'Adding full bibliography for 7063640--7063645.cif.'
_cod_database_code               7063643
_chemical_oxdiff_formula         'Co C10H10N3O9'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(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
 C9-N6 \\sim C9-N6A
 with sigma of 0.02
 N4-C16 \\sim N4-C16a
 with sigma of 0.02
 C16-C18 \\sim C16a-C18a
 with sigma of 0.02
 C16-C17 \\sim C16a-C17a
 with sigma of 0.02
 N4-C18 \\sim N4-C18a
 with sigma of 0.04
 N4-C17 \\sim N4-C17a
 with sigma of 0.04
 C18-C17 \\sim C18a-C17a
 with sigma of 0.04
 C18a-C16a \\sim C16a-C17a
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C16 \\sim C18 \\sim C17 \\sim C18a \\sim C16a \\sim C17a \\sim H16 \\sim H18a
\\sim H18c \\sim H17b \\sim H17c \\sim H18e \\sim H18f \\sim H16a \\sim H17d
\\sim H17e \\sim H17f \\sim H17a \\sim H18d \\sim H18b: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C23 \\sim C24 \\sim C22 \\sim C24A \\sim C22A \\sim C23A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
C23A \\sim C23 \\sim C22 \\sim C24 \\sim C24A \\sim C22A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C23) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 N4, C16a
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C16
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, C22, C24, N5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N6A)=Sof(H6Aa)=Sof(C10A)=Sof(H10A)=Sof(C12A)=Sof(H12a)=Sof(H12b)=
 Sof(H12c)=Sof(C11A)=Sof(H11a)=Sof(H11b)=Sof(H11c)=1-FVAR(1)
 Sof(N6)=Sof(H6)=Sof(C12)=Sof(H12d)=Sof(H12e)=Sof(H12f)=Sof(C10)=Sof(H10)=
 Sof(C11)=Sof(H11d)=Sof(H11e)=Sof(H11f)=FVAR(1)
 Sof(H5b)=Sof(C23A)=Sof(H23d)=Sof(H23e)=Sof(H23f)=Sof(C22A)=Sof(H22A)=
 Sof(C24A)=Sof(H24d)=Sof(H24e)=Sof(H24f)=1-FVAR(2)
 Sof(H5a)=Sof(C22)=Sof(H22)=Sof(C24)=Sof(H24a)=Sof(H24b)=Sof(H24c)=Sof(C23)=
 Sof(H23a)=Sof(H23b)=Sof(H23c)=FVAR(2)
 Sof(H4b)=Sof(C18a)=Sof(H18d)=Sof(H18e)=Sof(H18f)=Sof(C16a)=Sof(H16a)=
 Sof(C17a)=Sof(H17d)=Sof(H17e)=Sof(H17f)=1-FVAR(3)
 Sof(H4a)=Sof(C16)=Sof(H16)=Sof(C18)=Sof(H18a)=Sof(H18b)=Sof(H18c)=Sof(C17)=
 Sof(H17a)=Sof(H17b)=Sof(H17c)=FVAR(3)
 Sof(O10)=Sof(H10b)=Sof(H10c)=FVAR(4)
6.a Free rotating group:
 O10(H10b,H10c)
6.b Ternary CH refined with riding coordinates:
 C16(H16), C10A(H10A), C10(H10), C22(H22), C22A(H22A), C16a(H16a)
6.c Secondary CH2 refined with riding coordinates:
 C19(H19a,H19b), C6(H6a,H6b), C20(H20a,H20b), C5(H5c,H5d), C3(H3a,H3b), C4(H4c,
 H4d), C8(H8a,H8b), C7(H7a,H7b), C1(H1a,H1b), C14(H14a,H14b), C13(H13a,H13b),
 C2(H2a,H2b)
6.d Aromatic/amide H refined with riding coordinates:
 N4(H4a), N4(H4b), N5(H5a), N5(H5b), N6(H6), N6A(H6Aa)
6.e Idealised Me refined as rotating group:
 C18(H18a,H18b,H18c), C17(H17a,H17b,H17c), C12A(H12a,H12b,H12c), C11A(H11a,
 H11b,H11c), C12(H12d,H12e,H12f), C11(H11d,H11e,H11f), C24(H24a,H24b,H24c),
 C23(H23a,H23b,H23c), C23A(H23d,H23e,H23f), C24A(H24d,H24e,H24f), C18a(H18d,
 H18e,H18f), C17a(H17d,H17e,H17f)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.031
_oxdiff_exptl_absorpt_empirical_full_min 0.563