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_7718133
_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 H78 Cu2 N8 O2 P4, 2(Cl O4), 2.5[CH2Cl2]'
_chemical_formula_sum            'C92.5 H83 Cl7 Cu2 N8 O10 P4'
_chemical_formula_weight         1965.77
_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                 98.045(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.4571(3)
_cell_length_b                   24.5382(4)
_cell_length_c                   22.7738(4)
_cell_measurement_reflns_used    20928
_cell_measurement_temperature    99.98(15)
_cell_measurement_theta_max      67.5720
_cell_measurement_theta_min      3.2470
_cell_volume                     9106.2(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      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.985
_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    -31.00  24.00   0.50    1.80    --  -43.75  27.00 -42.00  110
  2  \w    -97.00 -70.00   0.50    1.80    --  -43.75 -27.00 155.00   54
  3  \w    -20.00  14.00   0.50    1.80    --   45.32 -27.00 155.00   68
  4  \w     49.00 104.00   0.50    1.80    --   45.32  27.00 -42.00  110
  5  \w   -147.00-122.00   0.50    6.50    --  -93.31 -27.00 155.00   50
  6  \w     87.00 150.00   0.50    6.50    --   94.87  27.00 -42.00  126
  7  \w    -59.00 -26.00   0.50    1.80    --  -43.75 -54.00   0.00   66
  8  \w    -97.00 -66.00   0.50    1.80    --  -43.75 138.00  60.00   62
  9  \w    -61.00 -30.00   0.50    1.80    --  -43.75 138.00  60.00   62
 10  \w    -34.00  20.00   0.50    1.80    --  -43.75  32.00-180.00  108
 11  \w   -103.00 -68.00   0.50    1.80    --  -43.75 -54.00   0.00   70
 12  \w    -96.00 -66.00   0.50    1.80    --  -43.75-138.00 -60.00   60
 13  \w   -102.00 -76.00   0.50    1.80    --  -43.75-138.00-180.00   52
 14  \w     34.00  65.00   0.50    1.80    --   45.32  43.00  60.00   62
 15  \w     84.00 112.00   0.50    1.80    --   45.32 138.00-120.00   56
 16  \w     65.00 108.00   0.50    1.80    --   45.32 138.00   0.00   86
 17  \w    -19.00  20.00   0.50    1.80    --   45.32 -11.00  90.00   78
 18  \w     -2.00  45.00   0.50    1.80    --   45.32 -43.00   0.00   94
 19  \w     82.00 108.00   0.50    1.80    --   45.32  43.00  60.00   52
 20  \w   -110.00 -29.00   0.50    6.50    --  -93.31 117.00 -30.00  162
 21  \w    -53.00 -27.00   0.50    6.50    --  -93.31  50.00 -90.00   52
 22  \w    -56.00 -30.00   0.50    6.50    --  -93.31 117.00   0.00   52
 23  \w   -161.00 -86.00   0.50    6.50    --  -93.31 -25.00  90.00  150
 24  \w    -53.00 -27.00   0.50    6.50    --  -93.31  50.00  90.00   52
 25  \w    -55.00 -29.00   0.50    6.50    --  -93.31  50.00-180.00   52
 26  \w   -158.00 -87.00   0.50    6.50    --  -93.31 -50.00-180.00  142
 27  \w   -157.00 -81.00   0.50    6.50    --  -93.31 -42.00  60.00  152
 28  \w    -69.00 -26.00   0.50    6.50    --  -93.31  59.00-120.00   86
 29  \w    -94.00 -27.00   0.50    6.50    --  -93.31  96.00 -30.00  134
 30  \w    -54.00 -29.00   0.50    6.50    --  -93.31  50.00-120.00   50
 31  \w   -103.00 -77.00   0.50    6.50    --  -93.31 -77.00 120.00   52
 32  \w   -152.00-119.00   0.50    6.50    --  -93.31 -77.00 120.00   66
 33  \w    -57.00 -32.00   0.50    6.50    --  -93.31  50.00-150.00   50
 34  \w    -78.00 -52.00   0.50    6.50    --  -93.31  68.00-120.00   52
 35  \w     31.00  56.00   0.50    6.50    --   94.87 -50.00  30.00   50
 36  \w     32.00  57.00   0.50    6.50    --   94.87 -50.00 -60.00   50
 37  \w     43.00  68.00   0.50    6.50    --   94.87 -68.00   0.00   50
 38  \w     27.00 103.00   0.50    6.50    --   94.87 -96.00  60.00  152
 39  \w    105.00 130.00   0.50    6.50    --   94.87  33.00 -90.00   50
;
_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  0.0420
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            55577
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.520
_diffrn_reflns_theta_min         3.256
_exptl_absorpt_coefficient_mu    3.643
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.597
_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    1.434
_exptl_crystal_description       irregular
_exptl_crystal_F_000             4044
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.876
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1051
_refine_ls_number_reflns         16531
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0798
_refine_ls_R_factor_gt           0.0660
_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^)+(0.0698P)^2^+19.6669P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1630
_refine_ls_wR_factor_ref         0.1715
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13218
_reflns_number_total             16531
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03137g3.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7718132--7718135.cif.'
_cod_original_formula_sum        'C92.50 H83 Cl7 Cu2 N8 O10 P4'
_cod_database_code               7718133
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.712
_shelx_estimated_absorpt_t_min   0.463
_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
 Cl2-O9 \\sim Cl2-O8A \\sim Cl2-O7 \\sim Cl2-O7A \\sim Cl2-O10 \\sim Cl2-O10A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O10) = Uanis(O7)
Uanis(O8A) = Uanis(O8) = Uanis(O10A) = Uanis(O7) = Uanis(O7A) = Uanis(O10)
4. Others
 Sof(O7A)=Sof(O10A)=Sof(O8A)=1-FVAR(1)
 Sof(O8)=Sof(O7)=Sof(O10)=FVAR(1)
5.a 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),
 C12(H12), C14(H14), C15(H15), C16(H16), C24(H24), C25(H25), C26(H26), C29(H29),
  C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C36(H36), C37(H37),
 C38(H38), C39(H39), C42(H42), C49(H49), C53(H53), C54(H54), C55(H55), C56(H56),
  C57(H57), C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C65(H65),
 C66(H66), C67(H67), C74(H74), C75(H75), C76(H76), C80(H80), C81(H81), C82(H82),
  C83(H83), C84(H84), C86(H86), C87(H87), C88(H88), C89(H89), C90(H90)
5.b Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C40(H40A,H40B,H40C), C44(H44A,H44B,
 H44C), C48(H48A,H48B,H48C), C51(H51A,H51B,H51C), C71(H71A,H71B,H71C), C72(H72A,
 H72B,H72C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 384 electrons were 
found in a volume of 1424\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2.5[CH2Cl2] per Asymmetric Unit 
which account for 360 electrons 
per unit cell.
;
_shelx_res_checksum              79369
_shelx_fab_checksum              49903
_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
;