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_7063642
_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         'C30 H36 N6 Ni O3, 2(N O3), 1.5[CH4O]'
_chemical_formula_sum            'C31.5 H42 N8 Ni O10.5'
_chemical_formula_weight         759.426
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_audit_creation_date             2024-08-08
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-25 deposited with the CCDC.	2025-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.999(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.2195(5)
_cell_length_b                   19.5074(8)
_cell_length_c                   11.0872(3)
_cell_measurement_reflns_used    10507
_cell_measurement_temperature    100
_cell_measurement_theta_max      27.2750
_cell_measurement_theta_min      2.1000
_cell_volume                     3488.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.00
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.9997
_diffrn_measured_fraction_theta_max 0.9994
_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    -98.00  22.00   0.50    3.00    --   -9.10 -57.00-120.00  240
  2  \w    -98.00  23.00   0.50    3.00    --   -9.10 -60.00   0.00  242
  3  \w    -98.00  49.00   0.50    3.00    --   -9.10 -19.00   0.00  294
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0579
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_Laue_measured_fraction_full 0.9997
_diffrn_reflns_Laue_measured_fraction_max 0.9994
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            45487
_diffrn_reflns_point_group_measured_fraction_full 0.9997
_diffrn_reflns_point_group_measured_fraction_max 0.9994
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         28.70
_diffrn_reflns_theta_min         2.09
_exptl_absorpt_coefficient_mu    0.625
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20464
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_description       block
_exptl_crystal_F_000             1598.644
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.9861
_refine_diff_density_min         -0.6632
_refine_diff_density_rms         0.1092
_refine_ls_d_res_high            0.7400
_refine_ls_d_res_low             9.7537
_refine_ls_goodness_of_fit_ref   1.0200
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_constraints    2
_refine_ls_number_parameters     755
_refine_ls_number_reflns         8997
_refine_ls_number_restraints     740
_refine_ls_restrained_S_all      0.9771
_refine_ls_R_factor_all          0.0879
_refine_ls_R_factor_gt           0.0549
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0682P)^2^+2.0657P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1302
_refine_ls_wR_factor_ref         0.1439
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              21
_reflns_limit_h_min              -21
_reflns_limit_k_max              26
_reflns_limit_k_min              0
_reflns_limit_l_max              14
_reflns_limit_l_min              0
_reflns_number_gt                6159
_reflns_number_total             8997
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4nj05327c2.cif
_cod_data_source_block           CG_Ni(L2)_1a
_cod_depositor_comments
'Adding full bibliography for 7063640--7063645.cif.'
_cod_original_formula_sum        'C31.5 H42 N8 Ni1 O10.5'
_cod_database_code               7063642
_olex2_refinement_description
;
1. Restrained distances
 O4-N8 \\sim O4A-N8
 with sigma of 0.02
2. Rigid body (RIGU) restrains
 Ni1, O1, O2, O3, N1, N2, N3, N4, H4, N5, H5, N6, H6, C1, H1a, H1b, C2, H2a,
 H2b, C3, H3a, H3b, C4, H4a, H4b, C5, H5a, H5b, C6, H6a, H6b, C7, H7a, H7b, C8,
 C9, C10, H10, C11, H11, C12, H12, C13, H13, C14, H14, C15, H15a, H15b, C16,
 C17, C18, H18, C19, H19, C20, H20, C21, H21, C22, H22, C23, H23a, H23b, C24,
 C25, C26, H26, C27, H27, C28, H28, C29, H29, C30, H30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(O4A)=1-FVAR(1)
 Sof(O4)=FVAR(1)
4.a Fitted hexagon refined as free rotating group:
 C22(C17,C18,C19,C20,C21)
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   High
   METHOD:         B3LYP
   BASIS SET:      def2-SVP
   CHARGE:         0
   MULTIPLICITY:   1
   DATE:           2024-08-08_13-29-09
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 102 electrons were 
found in a volume of 422\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1.5[CH4O] per formula unit 
which account for 108 electrons 
per unit cell.
;
_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
;