A novel type of heteroleptic Cu(I) complexes featuring nitrogen-rich tetrazine ligands: syntheses, crystal structures, spectral properties, cyclic voltammetry, and theoretical calculations.
Sztula, Adam; Antal, Peter; Nemec, Ivan; Kubala, Martin; Herchel, Radovan; Dalton transactions (Cambridge, England : 2003) 54 (2025) 5944–5952; doi:10.1039/d4dt03137g

data_7718132
_publ_section_title
;
 A novel type of heteroleptic Cu(I) complexes featuring nitrogen-rich
 tetrazine ligands: syntheses, crystal structures, spectral properties,
 cyclic voltammetry, and theoretical calculations.
;
_journal_issue                   14
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5944
_journal_page_last               5952
_journal_paper_doi               10.1039/d4dt03137g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C90 H72 Cu2 N6 O2 P4, 2(Cl O4), 2(C H2 Cl2)'
_chemical_formula_sum            'C92 H76 Cl6 Cu2 N6 O10 P4'
_chemical_formula_weight         1889.24
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-19
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2024-10-22 deposited with the CCDC.	2025-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.8590(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.39000(10)
_cell_length_b                   17.6750(2)
_cell_length_c                   20.9590(2)
_cell_measurement_reflns_used    17030
_cell_measurement_temperature    100.00(12)
_cell_measurement_theta_max      68.2520
_cell_measurement_theta_min      3.8820
_cell_volume                     4204.27(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.991
_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     73.00 105.00   0.50    1.60    --   94.87 -77.00 -30.00   64
  2  \w     30.00  56.00   0.50    1.60    --   94.87 -50.00 -30.00   52
  3  \w     32.00  57.00   0.50    1.60    --   94.87 -68.00   0.00   50
  4  \w     33.00  66.00   0.50    1.60    --   94.87 -59.00  90.00   66
  5  \w     29.00  56.00   0.50    1.60    --   94.87 -50.00 120.00   54
  6  \w     32.00  57.00   0.50    1.60    --   94.87 -50.00  90.00   50
  7  \w     30.00  57.00   0.50    1.60    --   94.87 -50.00  60.00   54
  8  \w     29.00  54.00   0.50    1.60    --   94.87 -50.00-150.00   50
  9  \w     69.00  94.00   0.50    0.50    --   45.32  36.00 -57.00   50
 10  \w     87.00 144.00   0.50    1.60    --   94.87  36.00 -57.00  114
 11  \w     86.00 155.00   0.50    1.60    --   94.87  33.00-120.00  138
 12  \w     89.00 153.00   0.50    1.60    --   94.87  33.00   0.00  128
 13  \w     87.00 152.00   0.50    1.60    --   94.87  33.00 150.00  130
 14  \w    -12.00  15.00   0.50    0.50    --   45.32 -32.00 150.00   54
 15  \w     -6.00  19.00   0.50    0.50    --   45.32 -36.00 146.00   50
 16  \w     23.00  67.00   0.50    0.50    --   45.32 -65.00  30.00   88
 17  \w     64.00 112.00   0.50    0.50    --   45.32 138.00 150.00   96
 18  \w     68.00 112.00   0.50    0.50    --   45.32 138.00  30.00   88
 19  \w    -12.00  21.00   0.50    0.50    --   45.32 -65.00  30.00   66
 20  \w     -7.00  20.00   0.50    0.50    --   45.32 -32.00  90.00   54
 21  \w     48.00  73.00   0.50    1.60    --   94.87-117.00 120.00   50
 22  \w    -25.00  30.00   0.50    0.50    --  -43.75  11.00  60.00  110
 23  \w    -49.00  12.00   0.50    0.50    --  -43.75  54.00 120.00  122
 24  \w     54.00 123.00   0.50    1.60    --   94.87 -86.00-150.00  138
 25  \w    -40.00  10.00   0.50    0.50    --  -43.75  36.00 -57.00  100
 26  \w    -40.00   4.00   0.50    0.50    --  -43.75  43.00-180.00   88
 27  \w    -57.00 -32.00   0.50    1.60    --  -93.31  50.00 -60.00   50
 28  \w    -83.00 -48.00   0.50    1.60    --  -93.31  68.00 -90.00   70
 29  \w    -73.00 -28.00   0.50    1.60    --  -93.31  68.00 -30.00   90
 30  \w    -55.00 -29.00   0.50    1.60    --  -93.31  50.00  60.00   52
 31  \w    -75.00 -43.00   0.50    1.60    --  -93.31  68.00  90.00   64
 32  \w   -104.00 -41.00   0.50    1.60    --  -93.31  77.00 150.00  126
 33  \w    -83.00 -51.00   0.50    1.60    --  -93.31  68.00 150.00   64
 34  \w   -116.00 -91.00   0.50    1.60    --  -93.31 -36.00 146.00   50
 35  \w    -90.00 -64.00   0.50    0.50    --  -43.75-138.00 -30.00   52
 36  \w   -103.00 -68.00   0.50    0.50    --  -43.75-138.00-150.00   70
 37  \w    -90.00 -63.00   0.50    0.50    --  -43.75 -36.00 146.00   54
 38  \w   -109.00 -29.00   0.50    1.60    --  -93.31 117.00 -60.00  160
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1296662000
_diffrn_orient_matrix_UB_12      0.0151088000
_diffrn_orient_matrix_UB_13      0.0236744000
_diffrn_orient_matrix_UB_21      -0.0344520000
_diffrn_orient_matrix_UB_22      0.0783623000
_diffrn_orient_matrix_UB_23      0.0247208000
_diffrn_orient_matrix_UB_31      -0.0208171000
_diffrn_orient_matrix_UB_32      -0.0350695000
_diffrn_orient_matrix_UB_33      0.0653277000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0340
_diffrn_reflns_av_unetI/netI     0.0305
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            24899
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.414
_diffrn_reflns_theta_min         3.276
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.630
_exptl_absorpt_correction_T_max  0.809
_exptl_absorpt_correction_T_min  0.511
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.57a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.492
_exptl_crystal_description       prism
_exptl_crystal_F_000             1940
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.18
_refine_diff_density_max         1.722
_refine_diff_density_min         -1.120
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         7670
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0813P)^2^+4.5560P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1376
_refine_ls_wR_factor_ref         0.1420
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6838
_reflns_number_total             7670
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03137g3.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7718132--7718135.cif.'
_cod_original_cell_volume        4204.26(7)
_cod_database_code               7718132
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C184  H152  Cl12  Cu4  N12  O20  P8  '
_shelx_estimated_absorpt_t_max   0.561
_shelx_estimated_absorpt_t_min   0.419
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
2.a Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C13(H13), C14(H14), C15(H15), C019(H019), C22(H22), C23(H23), C24(H24),
 C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C34(H34), C35(H35), C36(H36),
  C37(H37), C38(H38), C40(H40), C42(H42), C43(H43), C44(H44)
2.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              33345
_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 1.415
_oxdiff_exptl_absorpt_empirical_full_min 0.787