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_7063645
_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
'3(C30 H36 Cu N6 O3), 6(N O3), C4 H10 O, 1[CH4O], 0.25[C4H10O]'
_chemical_formula_sum            'C96 H124.5 Cu3 N24 O29.25'
_chemical_formula_weight         2273.340
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_audit_creation_date             2025-02-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-05 deposited with the CCDC.	2025-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                85.355(1)
_cell_angle_beta                 80.554(1)
_cell_angle_gamma                60.327(2)
_cell_formula_units_Z            2
_cell_length_a                   17.6146(3)
_cell_length_b                   17.6300(3)
_cell_length_c                   20.0301(3)
_cell_measurement_reflns_used    36247
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      29.3320
_cell_measurement_theta_min      1.6890
_cell_volume                     5331.28(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (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 0.9991
_diffrn_measured_fraction_theta_max 0.9993
_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    -56.00   9.00   0.50   15.00    --  -18.50 -57.00 120.00  130
  2  \w     22.00  64.00   0.50   15.00    --  -18.50  19.00  90.00   84
  3  \w    -51.00  24.00   0.50   15.00    --  -18.50  77.00 -30.00  150
  4  \w    -16.00  64.00   0.50   15.00    --  -18.50  38.00  60.00  160
  5  \w    -30.00  -3.00   0.50   15.00    --   21.15 114.00  90.62   54
  6  \w    -18.00  54.00   0.50   15.00    --   21.15 -77.00  90.00  144
  7  \w    -36.00 -10.00   0.50   15.00    --   21.15 124.00 107.89   52
  8  \w    -67.00 -16.00   0.50   15.00    --   21.15 -19.00-150.00  102
  9  \w      0.00  65.00   0.50   15.00    --   21.15 -99.00 150.00  130
 10  \w    -33.00  -7.00   0.50   15.00    --   21.15 119.00 -92.58   52
 11  \w    -67.00 -16.00   0.50   15.00    --   21.15 -19.00-180.00  102
 12  \w     -7.00 104.00   0.50   15.00    --   21.15  38.00 -30.00  222
 13  \w    -56.00   9.00   0.50   15.00    --  -18.50 -57.00 -90.00  130
 14  \w   -107.00 -16.00   0.50   15.00    --  -18.50 -19.00 150.00  182
 15  \w    -51.00  24.00   0.50   15.00    --  -18.50  77.00 -90.00  150
 16  \w    -38.00 -12.00   0.50   15.00    --   21.15 127.00  41.13   52
 17  \w     -6.00  62.00   0.50   15.00    --   21.15  57.00 150.00  136
 18  \w      0.00  65.00   0.50   15.00    --   21.15 -99.00-150.00  130
 19  \w    -67.00 -16.00   0.50   15.00    --   21.15 -19.00 -90.00  102
;
_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  0.0673
_diffrn_reflns_av_unetI/netI     0.0628
_diffrn_reflns_Laue_measured_fraction_full 0.9991
_diffrn_reflns_Laue_measured_fraction_max 0.9993
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            124966
_diffrn_reflns_point_group_measured_fraction_full 0.9991
_diffrn_reflns_point_group_measured_fraction_max 0.9993
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         28.70
_diffrn_reflns_theta_min         1.68
_exptl_absorpt_coefficient_mu    0.681
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70174
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.416
_exptl_crystal_description       cube
_exptl_crystal_F_000             2382.868
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.8863
_refine_diff_density_min         -0.6467
_refine_diff_density_rms         0.1183
_refine_ls_d_res_high            0.7400
_refine_ls_d_res_low             12.1043
_refine_ls_goodness_of_fit_ref   1.0385
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    202
_refine_ls_number_parameters     1464
_refine_ls_number_reflns         27524
_refine_ls_number_restraints     384
_refine_ls_restrained_S_all      1.0310
_refine_ls_R_factor_all          0.0955
_refine_ls_R_factor_gt           0.0578
_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^)+(0.0647P)^2^+3.1767P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1362
_refine_ls_wR_factor_ref         0.1537
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              23
_reflns_limit_h_min              -23
_reflns_limit_k_max              23
_reflns_limit_k_min              -23
_reflns_limit_l_max              27
_reflns_limit_l_min              0
_reflns_number_gt                18228
_reflns_number_total             27524
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d4nj05327c2.cif
_cod_data_source_block           2021_DPT_GR_CBG_Cu_LigandA_auto
_cod_depositor_comments
'Adding full bibliography for 7063640--7063645.cif.'
_cod_database_code               7063645
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H42 of C42, H41 of C41, H59 of C59, H50 of C50, H51 of
  C51, H44 of C44, H45 of C45, H58 of C58, H49 of C49, H60 of C60, H52 of C52,
  H26 of C26, H43 of C43, H57 of C57, H53 of C53, H61 of C61, H13 of C13, H18
  of C18, H29 of C29, H31 of C31, H10 of C10, H30 of C30, H28 of C28, H21 of
  C21, H12 of C12, H20 of C20, H14 of C14, H22 of C22, H19 of C19, H11 of C11,
  H27 of C27, H90 of C90, H89 of C89, H88 of C88, H82 of C82, H87 of C87, H80
  of C80, H72 of C72, H74 of C74, H75 of C75, H83 of C83, H73 of C73, H81 of
  C81, H71 of C71, H79 of C79, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H91a of C91
2. Restrained distances
 C93-H93a
 1.046 with sigma of 0.02
 N103-O108 = N103-O109
 1.25 with sigma of 0.02
 N103-O107
 1.24 with sigma of 0.02
 O14-N1a
 1.25 with sigma of 0.005
 O15-N1a
 1.25 with sigma of 0.005
 N1a-O13
 1.25 with sigma of 0.005
 O104-N102
 1.25 with sigma of 0.01
 O105-N102
 1.25 with sigma of 0.01
 N1b-O18
 1.25 with sigma of 0.01
 N1b-O17
 1.25 with sigma of 0.01
 O108-N103
 1.25 with sigma of 0.01
 O10-N19
 1.25 with sigma of 0.01
 N1b-O16
 1.25 with sigma of 0.02
 O16-N1b
 1.25 with sigma of 0.005
 O105-N102 \\sim O13-N102
 with sigma of 0.02
 O104-N102 \\sim O14-N102
 with sigma of 0.02
 O106-N102 \\sim O15-N102
 with sigma of 0.02
 O13-N102 \\sim O13-N1a
 with sigma of 0.02
 O15-N102 \\sim O15-N1a
 with sigma of 0.02
 O14-N102 \\sim O14-N1a
 with sigma of 0.02
 O104-N102 \\sim O104-N1a
 with sigma of 0.02
 O108-O107 \\sim O107-O109 \\sim O109-O108
 with sigma of 0.04
 O105-N102 \\sim O105-N1a
 with sigma of 0.02
 O106-N102 \\sim O106-N1a
 with sigma of 0.02
 N103-O108 \\sim N103-O107 \\sim N103-O109
 with sigma of 0.02
 O107-N103 \\sim O16-N1b
 with sigma of 0.02
 O108-N103 \\sim O17-N1b
 with sigma of 0.02
 O109-N103 \\sim O18-N1b
 with sigma of 0.02
 O107-O108 \\sim O16-O17
 with sigma of 0.04
 O107-O109 \\sim O16-O18
 with sigma of 0.04
 O108-O109 \\sim O17-O18
 with sigma of 0.04
 O101-N101 \\sim O10-N19
 with sigma of 0.02
 O102-N101 \\sim O11-N19
 with sigma of 0.02
 O103-N101 \\sim O12-N19
 with sigma of 0.02
 O101-O102 \\sim O10-O11
 with sigma of 0.04
 O101-O103 \\sim O10-O12
 with sigma of 0.04
 O102-O103 \\sim O11-O12
 with sigma of 0.04
 O11-N19 \\sim N19-O10
 with sigma of 0.02
 O11-O12 \\sim O12-O10
 with sigma of 0.005
3. Restrained planarity
 O104, O105, O106, N102
 with sigma of 0.1
 O107, O108, O109, N103
 with sigma of 0.1
 O13, O14, O15, N1a
 with sigma of 0.005
 O10, O11, O12, N19
 with sigma of 0.1
 O16, O17, O18, N1b
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O107 \\sim O108 \\sim O109 \\sim N103: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O107 \\sim O108 \\sim O109 \\sim N103 \\sim O16 \\sim O17 \\sim O18 \\sim N1b:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C91 \\sim C92: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
O101 \\sim O102 \\sim O103 \\sim N101 \\sim O10 \\sim O11 \\sim O12 \\sim N19:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(N102) = Uanis(N1a)
5. Rigid body (RIGU) restrains
 O101, O102, O103, N101
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O107, O108, O109, N103
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O101, O102, O103, N101, O10, O11, O12, N19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O16, O17, O18, N1b
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Others
 Sof(O13)=Sof(O14)=Sof(O15)=Sof(N1a)=1-FVAR(1)
 Sof(O104)=Sof(O105)=Sof(O106)=Sof(N102)=FVAR(1)
 Sof(O16)=Sof(O17)=Sof(O18)=Sof(N1b)=1-FVAR(2)
 Sof(O107)=Sof(O108)=Sof(O109)=Sof(N103)=FVAR(2)
 Sof(O10)=Sof(O11)=Sof(O12)=Sof(N19)=1-FVAR(3)
 Sof(O101)=Sof(O102)=Sof(O103)=Sof(N101)=FVAR(3)
7.a 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), C15(H15a,H15b), C23(H23a,H23b), C32(H32a,H32b), C33(H33a,H33b),
 C34(H34a,H34b), C35(H35a,H35b), C36(H36a,H36b), C37(H37a,H37b), C38(H38a,H38b),
  C46(H46a,H46b), C54(H54a,H54b), C62(H62a,H62b), C63(H63a,H63b), C64(H64a,
 H64b), C65(H65a,H65b), C66(H66a,H66b), C67(H67a,H67b), C68(H68a,H68b),
 C76(H76a,H76b), C84(H84a,H84b)
7.b Aromatic/amide H refined with riding coordinates:
 N4(H4), N5(H5), N6(H6), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C27(H27), C28(H28), C29(H29),
  C30(H30), C31(H31), N10(H10a), N11(H11a), N12(H12a), C41(H41), C42(H42),
 C43(H43), C44(H44), C45(H45), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53),
  C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), N16(H16), N17(H17),
 N18(H18a), C26(H26), C71(H71), C72(H72), C73(H73), C74(H74), C75(H75),
 C79(H79), C80(H80), C81(H81), C82(H82), C83(H83), C87(H87), C88(H88), C89(H89),
  C90(H90)
7.c Idealised Me refined as rotating group:
 C92(H92a,H92b,H92c), C94(H94a,H94b,H94c)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 58 electrons were 
found in a volume of 253\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[CH3OH], 0.25[C4H10O] per Asymmetric Unit 
which account for 57 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
;