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_7718135
_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 H40 Cu N6 O P2, Cl O4, 1.5(C H Cl3), 0.5[CHCl3]'
_chemical_formula_sum            'C48 H42 Cl7 Cu N6 O5 P2'
_chemical_formula_weight         1156.50
_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
_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                 98.8230(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.4022(2)
_cell_length_b                   30.4917(5)
_cell_length_c                   24.3287(4)
_cell_measurement_reflns_used    21268
_cell_measurement_temperature    89.9(3)
_cell_measurement_theta_max      67.8490
_cell_measurement_theta_min      3.4040
_cell_volume                     10557.5(3)
_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      90.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.986
_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    -84.00 -32.00   0.50    6.00    --  -43.63 124.00  56.00  104
  2  \w    -89.00 -57.00   0.50    6.00    --  -43.63 146.00-137.00   64
  3  \w   -110.00 -64.00   0.50    6.00    --  -43.63-146.00 171.00   92
  4  \w     18.00  62.00   0.50    6.00    --   45.19-124.00 -22.00   88
  5  \w     39.00  87.00   0.50    6.00    --   45.19-146.00 171.00   96
  6  \w     61.00  86.00   0.50    6.00    --   45.19 146.00-137.00   50
  7  \w   -138.00-110.00   0.50   30.00    --  -93.31-124.00 -22.00   56
  8  \w   -126.00 -68.00   0.50   30.00    --  -93.31 146.00-137.00  116
  9  \w     95.00 123.00   0.50   30.00    --   94.87 124.00  56.00   56
 10  \w     73.00 126.00   0.50   30.00    --   94.87-146.00 171.00  106
 11  \w   -105.00 -50.00   0.50    6.00    --  -43.63 -43.00  60.00  110
 12  \w    -24.00  25.00   0.50    6.00    --  -43.63  11.00-180.00   98
 13  \w    -26.00  26.00   0.50    6.00    --  -43.63  21.00  60.00  104
 14  \w     78.00 106.00   0.50    6.00    --   45.19  77.00   0.00   56
 15  \w     23.00  51.00   0.50    6.00    --   45.19  77.00   0.00   56
 16  \w     -8.00  26.00   0.50    6.00    --   45.19 -21.00 -30.00   68
 17  \w     53.00 109.00   0.50    6.00    --   45.19  32.00-180.00  112
 18  \w    -19.00  28.00   0.50    6.00    --   45.19 -32.00  30.00   94
 19  \w    -22.00  28.00   0.50    6.00    --   45.19 -21.00-150.00  100
 20  \w   -106.00 -27.00   0.50   30.00    --  -93.31  77.00  90.00  158
 21  \w    -81.00 -50.00   0.50   30.00    --  -93.31  68.00  30.00   62
 22  \w    -54.00 -27.00   0.50   30.00    --  -93.31  50.00-150.00   54
 23  \w   -158.00 -84.00   0.50   30.00    --  -93.31 -50.00 -30.00  148
 24  \w   -156.00 -78.00   0.50   30.00    --  -93.31 -86.00  60.00  156
 25  \w     87.00 121.00   0.50   30.00    --   94.87  33.00 120.00   68
 26  \w     49.00 106.00   0.50   30.00    --   94.87 -96.00 -30.00  114
 27  \w     30.00  57.00   0.50   30.00    --   94.87 -50.00 -30.00   54
 28  \w     29.00  55.00   0.50   30.00    --   94.87 -50.00-120.00   52
 29  \w     29.00  57.00   0.50   30.00    --   94.87 -50.00  30.00   56
 30  \w     31.00  68.00   0.50   30.00    --   94.87 -59.00 -60.00   74
 31  \w     74.00  99.00   0.50   30.00    --   94.87-117.00-180.00   50
 32  \w     30.00  58.00   0.50   30.00    --   94.87-117.00-180.00   56
 33  \w     29.00  56.00   0.50   30.00    --   94.87 -50.00-180.00   54
 34  \w    135.00 163.00   0.50   30.00    --   94.87  25.00 -30.00   56
 35  \w     86.00 120.00   0.50   30.00    --   94.87  25.00 -30.00   68
 36  \w     29.00  56.00   0.50   30.00    --   94.87 -50.00 -90.00   54
 37  \w     35.00  69.00   0.50   30.00    --   94.87 -59.00   0.00   68
 38  \w     76.00 156.00   0.50   30.00    --   94.87  59.00 150.00  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_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0594
_diffrn_reflns_av_unetI/netI     0.0534
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            61142
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.520
_diffrn_reflns_theta_min         3.427
_exptl_absorpt_coefficient_mu    4.835
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.403
_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    1.455
_exptl_crystal_description       prism
_exptl_crystal_F_000             4720
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.418
_refine_diff_density_min         -0.881
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1259
_refine_ls_number_reflns         19193
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.1094
_refine_ls_R_factor_gt           0.0827
_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^)+(0.0482P)^2^+94.9181P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2046
_refine_ls_wR_factor_ref         0.2200
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13783
_reflns_number_total             19193
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03137g3.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 7718132--7718135.cif.'
_cod_database_code               7718135
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.670
_shelx_estimated_absorpt_t_min   0.345
_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
 Cl10-O7 \\sim Cl10-O7A
 with sigma of 0.02
 Cl1-O6 \\sim Cl1A-O6 \\sim Cl1-O3 \\sim Cl1A-O3 \\sim Cl1-O5 \\sim Cl1A-O5A
\\sim Cl1-O4 \\sim Cl1A-O4A
 with sigma of 0.02
 Cl10-O10 \\sim Cl10-O10A
 with sigma of 0.02
 Cl10-O9 \\sim Cl10-O9A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O4 \\sim O4A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
O9A \\sim O9 \\sim O7A \\sim O7 \\sim O10A \\sim O10: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(Cl1) = Uanis(Cl1A)
Uanis(O5) = Uanis(O5A)
4. Others
 Sof(O9A)=Sof(O10A)=Sof(O7A)=1-FVAR(1)
 Sof(O7)=Sof(O9)=Sof(O10)=FVAR(1)
 Sof(Cl1A)=Sof(O4A)=Sof(O5A)=1-FVAR(2)
 Sof(Cl1)=Sof(O5)=Sof(O4)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C88(H88), C86(H86), C87(H87)
5.b Aromatic/amide H refined with riding coordinates:
 C85(H85), C25(H25), C83(H83), C84(H84), C16(H16), C23(H23), C24(H24),
 C14(H14), C39(H39), C48(H48), C32(H32), C72(H72), C70(H70), C73(H73), C66(H66),
  C31(H31), C29(H29), C52(H52), C49(H49), C2(H2), C74(H74), C38(H38), C28(H28),
 C8(H8), C12(H12), C60(H60), C02L(H02L), C64(H64), C50(H50), C6(H6), C54(H54),
 C68(H68), C15(H15), C51(H51), C67(H67), C69(H69), C37(H37), C11(H11), C61(H61),
  C35(H35), C30(H30), C62(H62), C46(H46), C9(H9), C42(H42), C36(H36), C58(H58),
 C3(H3), C63(H63), C10(H10), C56(H56), C57(H57), C92(H92), C55(H55), C5(H5),
 C4(H4)
5.c Idealised Me refined as rotating group:
 C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C44(H44A,H44B,H44C), C20(H20A,H20B,
 H20C), C40(H40A,H40B,H40C), C21(H21A,H21B,H21C), C90(H90A,H90B,H90C), C94(H94A,
 H94B,H94C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 236 electrons were 
found in a volume of 1102\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
0.5[CHCl3] per Asymmetric Unit 
which account for 232 electrons 
per unit cell.
;
_shelx_res_checksum              9721
_shelx_fab_checksum              62046
_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
;