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_7718134
_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         'C46 H37 Cu N5 O P2, Cl O4, 0.5[CHCl3]'
_chemical_formula_sum            'C46.5 H37.5 Cl2.5 Cu N5 O5 P2'
_chemical_formula_weight         960.42
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-10-22 deposited with the CCDC.	2025-02-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.3090(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.69420(10)
_cell_length_b                   15.04390(10)
_cell_length_c                   25.7657(2)
_cell_measurement_reflns_used    14816
_cell_measurement_temperature    297.8(3)
_cell_measurement_theta_max      69.5420
_cell_measurement_theta_min      3.4090
_cell_volume                     4473.17(6)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_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    -71.00 -29.00   0.50    0.60    --  -42.75  90.00-170.00   84
  2  \w    -20.00  18.00   0.50    0.60    --  -42.75  90.00-170.00   76
  3  \w     14.00  69.00   0.50    0.60    --   44.32 -90.00  74.00  110
  4  \w    -20.00   6.00   0.50    0.60    --   44.32 -90.00  74.00   52
  5  \w    -84.00 -47.00   0.50    4.00    --  -95.95  90.00-170.00   74
  6  \w    122.00 147.00   0.50    4.00    --   97.51  90.00-170.00   50
  7  \w   -109.00 -66.00   0.50    0.60    --  -42.75-138.00-150.00   86
  8  \w    -22.00  24.00   0.50    0.60    --  -42.75  21.00-180.00   92
  9  \w    -99.00 -73.00   0.50    0.60    --  -42.75 138.00  30.00   52
 10  \w    -26.00  -1.00   0.50    0.60    --  -42.75  21.00   0.00   50
 11  \w    -22.00   9.00   0.50    0.60    --  -42.75  21.00 150.00   62
 12  \w    -51.00 -25.00   0.50    0.60    --  -42.75 138.00  30.00   52
 13  \w    -33.00   4.00   0.50    0.60    --  -42.75  32.00 -60.00   74
 14  \w    -19.00  37.00   0.50    0.60    --   44.32 -32.00 120.00  112
 15  \w    -18.00  28.00   0.50    0.60    --   44.32 -32.00   0.00   92
 16  \w     50.00  92.00   0.50    0.60    --   44.32  43.00-150.00   84
 17  \w    -28.00  15.00   0.50    0.60    --   44.32 -11.00-120.00   86
 18  \w     73.00  99.00   0.50    0.60    --   44.32 138.00 -60.00   52
 19  \w    -57.00 -29.00   0.50    4.00    --  -95.95  50.00 120.00   56
 20  \w    -56.00 -29.00   0.50    4.00    --  -95.95  50.00 -60.00   54
 21  \w    -82.00 -29.00   0.50    4.00    --  -95.95  68.00  30.00  106
 22  \w    -57.00 -32.00   0.50    4.00    --  -95.95  50.00  30.00   50
 23  \w    -57.00 -29.00   0.50    4.00    --  -95.95  50.00-180.00   56
 24  \w    -57.00 -32.00   0.50    4.00    --  -95.95  50.00-150.00   50
 25  \w    -57.00 -29.00   0.50    4.00    --  -95.95  50.00 150.00   56
 26  \w   -146.00 -79.00   0.50    4.00    --  -95.95-117.00 120.00  134
 27  \w   -162.00-107.00   0.50    4.00    --  -95.95 -90.00  74.00  110
 28  \w     27.00  61.00   0.50    4.00    --   97.51 -96.00 120.00   68
 29  \w     31.00  56.00   0.50    4.00    --   97.51 -50.00 -60.00   50
 30  \w     52.00  84.00   0.50    4.00    --   97.51 -77.00-120.00   64
 31  \w     31.00  56.00   0.50    4.00    --   97.51 -50.00 -90.00   50
 32  \w     33.00  63.00   0.50    4.00    --   97.51 -59.00 -30.00   60
 33  \w     92.00 153.00   0.50    4.00    --   97.51  50.00 120.00  122
 34  \w     39.00  64.00   0.50    4.00    --   97.51 -59.00 -60.00   50
 35  \w     31.00  56.00   0.50    4.00    --   97.51 -50.00-120.00   50
 36  \w     72.00 107.00   0.50    4.00    --   97.51 -96.00 120.00   70
 37  \w     37.00  69.00   0.50    4.00    --   97.51 -59.00 120.00   64
 38  \w     78.00 161.00   0.50    4.00    --   97.51  68.00-180.00  166
 39  \w    104.00 150.00   0.50    4.00    --   97.51  33.00 150.00   92
 40  \w     54.00  79.00   0.50    4.00    --   97.51 -68.00  90.00   50
 41  \w     31.00  88.00   0.50    4.00    --   97.51 -90.00  74.00  114
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0229
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            27755
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.657
_diffrn_reflns_theta_min         3.414
_exptl_absorpt_coefficient_mu    3.167
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.426
_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    1.426
_exptl_crystal_description       prism
_exptl_crystal_F_000             1972
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.282
_refine_diff_density_min         -0.363
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     583
_refine_ls_number_reflns         8373
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0454
_refine_ls_R_factor_gt           0.0407
_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^)+(0.0612P)^2^+1.5169P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1147
_refine_ls_wR_factor_ref         0.1178
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7347
_reflns_number_total             8373
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03137g3.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7718132--7718135.cif.'
_cod_original_formula_sum        'C46.50 H37.50 Cl2.50 Cu N5 O5 P2'
_cod_database_code               7718134
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.665
_shelx_estimated_absorpt_t_min   0.460
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl1-O6 \\sim Cl1-O4 \\sim Cl1-O3 \\sim Cl1-O5
 with sigma of 0.02
 Cl1A-O6A \\sim Cl1A-O4A \\sim Cl1A-O3A \\sim Cl1A-O5A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O5 \\sim O5A \\sim O3 \\sim O3A \\sim O4 \\sim O4A \\sim O6 \\sim O6A: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(Cl1) = Uanis(Cl1A)
4. Others
 Sof(O3A)=Sof(O5A)=Sof(O6A)=Sof(O4A)=Sof(Cl1A)=1-FVAR(1)
 Sof(Cl1)=Sof(O5)=Sof(O6)=Sof(O4)=Sof(O3)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C6(H6), C14(H14), C28(H28), C16(H16), C25(H25), C15(H15), C12(H12),
 C43(H43), C33(H33), C27(H27), C32(H32), C26(H26), C30(H30), C5(H5), C39(H39),
 C4(H4), C9(H9), C46(H46), C10(H10), C31(H31), C2(H2), C11(H11), C35(H35),
 C3(H3), C36(H36), C37(H37), C40(H40), C44(H44), C38(H38), C45(H45)
5.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 122 electrons were 
found in a volume of 468\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.5[CHCl3] per formula unit 
which account for 116 electrons 
per unit cell.
;
_shelx_res_checksum              56516
_shelx_fab_checksum              7407
_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
;