Copper(II) Complexes of Dipica and Its Derivatives as Biomimetic Models for Phenoxazinone Synthase: Probing the Effect of Central N-cycloalkyl Rings on Reactivity
Ganesh, Yamuna; Devaraj , Karthickram; Palani, Narasimman; Bhuvanesh, Nattamai S. P.; Karuppasamy, Sundaravel; New Journal of Chemistry  (2026) –; doi:10.1039/D5NJ04085J

data_7064209
_publ_section_title
;
 Copper(II) Complexes of Dipica and Its Derivatives as Biomimetic Models
 for Phenoxazinone Synthase: Probing the Effect of Central N-cycloalkyl
 Rings on Reactivity
;
_journal_name_full               'New Journal of Chemistry'
_journal_paper_doi               10.1039/D5NJ04085J
_journal_year                    2026
_chemical_formula_moiety         'C17 H21 Cl2 Cu N3'
_chemical_formula_sum            'C17 H21 Cl2 Cu N3'
_chemical_formula_weight         401.81
_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             2024-05-29
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-10-14 deposited with the CCDC.	2025-12-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.4400(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.01600(10)
_cell_length_b                   13.9160(2)
_cell_length_c                   15.2343(2)
_cell_measurement_reflns_used    14101
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.6650
_cell_measurement_theta_min      4.3330
_cell_volume                     1697.86(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.103a 64-bit (release 20-12-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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     35.00 121.00   0.50    0.10    --   48.16  47.00 106.59  172
  2  \w     36.00  85.00   0.50    0.10    --   48.16  47.00 106.59   98
  3  \w    -17.00  11.00   0.50    0.10    --   48.16 -19.00 120.00   56
  4  \w    -23.00  12.00   0.50    0.10    --   48.16 -19.00 -30.00   70
  5  \w    -26.00  25.00   0.50    0.10    --   48.16 -28.00-104.00  102
  6  \w     39.00  71.00   0.50    0.10    --   48.16  47.00-147.63   64
  7  \w     36.00 116.00   0.50    0.10    --   48.16  45.00-172.80  160
  8  \w     51.00 100.00   0.50    0.10    --   48.16  46.00-128.46   98
  9  \w     36.00 122.00   0.50    0.10    --   48.16  28.00  57.00  172
 10  \w     36.00 120.00   0.50    0.10    --   48.16  45.00 170.73  168
 11  \w     95.00 120.00   0.50    0.10    --   48.16  45.00 170.73   50
 12  \w    112.00 165.00   0.50    0.50    --  113.25  77.00  60.00  106
 13  \w    138.00 178.00   0.50    0.50    --  113.25  61.00  90.00   80
 14  \w    106.00 132.00   0.50    0.50    --  113.25  61.00  90.00   52
 15  \w    106.00 135.00   0.50    0.50    --  113.25  61.00 120.00   58
 16  \w    140.00 175.00   0.50    0.50    --  113.25  61.00 120.00   70
 17  \w    107.00 152.00   0.50    0.50    --  113.25  61.00 150.00   90
 18  \w    105.00 135.00   0.50    0.50    --  113.25  45.00 120.00   60
 19  \w    103.00 129.00   0.50    0.50    --  113.25  45.00 150.00   52
 20  \w    102.00 163.00   0.50    0.50    --  113.25  45.00-120.00  122
 21  \w    152.00 178.00   0.50    0.50    --  113.25  45.00-150.00   52
 22  \w    106.00 137.00   0.50    0.50    --  113.25  61.00-180.00   62
 23  \w    101.00 127.00   0.50    0.50    --  113.25  45.00-180.00   52
 24  \w    128.00 154.00   0.50    0.50    --  113.25  45.00-180.00   52
 25  \w    106.00 139.00   0.50    0.50    --  113.25  61.00-150.00   66
 26  \w    101.00 131.00   0.50    0.50    --  113.25  45.00-150.00   60
 27  \w    102.00 135.00   0.50    0.50    --  113.25  15.00 -30.00   66
 28  \w    105.00 140.00   0.50    0.50    --  113.25  30.00  30.00   70
 29  \w    101.00 178.00   0.50    0.50    --  113.25  28.00  57.00  154
 30  \w    142.00 168.00   0.50    0.50    --  113.25  30.00  30.00   52
 31  \w     43.00  75.00   0.50    0.50    --  113.25 -61.00   0.00   64
 32  \w     47.00  73.00   0.50    0.50    --  113.25 -61.00  60.00   52
 33  \w     45.00  72.00   0.50    0.50    --  113.25 -61.00  90.00   54
 34  \w     44.00  70.00   0.50    0.50    --  113.25 -61.00 150.00   52
 35  \w     46.00  74.00   0.50    0.50    --  113.25 -61.00 -30.00   56
 36  \w     47.00  75.00   0.50    0.50    --  113.25 -61.00-180.00   56
 37  \w     42.00  95.00   0.50    0.50    --  113.25 -95.00 -90.00  106
 38  \w     45.00 109.00   0.50    0.50    --  113.25-125.00-180.00  128
 39  \w     71.00 104.00   0.50    0.50    --  113.25 -95.00 -60.00   66
 40  \w     42.00 105.00   0.50    0.50    --  113.25 -95.00 -30.00  126
 41  \w     45.00  70.00   0.50    0.50    --  113.25-125.00  30.00   50
 42  \w     74.00 105.00   0.50    0.50    --  113.25 -95.00  30.00   62
 43  \w     78.00 106.00   0.50    0.50    --  113.25 -95.00  90.00   56
 44  \w     42.00  70.00   0.50    0.50    --  113.25 -95.00  90.00   56
 45  \w     49.00  74.00   0.50    0.50    --  113.25 -95.00  60.00   50
 46  \w    -25.00  26.00   0.50    0.10    --  -48.16  28.00  57.00  102
 47  \w    -49.00 -20.00   0.50    0.50    --  -91.75  45.00 -90.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1381582000
_diffrn_orient_matrix_UB_12      0.0367925000
_diffrn_orient_matrix_UB_13      -0.0586452000
_diffrn_orient_matrix_UB_21      0.1308169000
_diffrn_orient_matrix_UB_22      -0.0163663000
_diffrn_orient_matrix_UB_23      0.0755769000
_diffrn_orient_matrix_UB_31      0.0284015000
_diffrn_orient_matrix_UB_32      -0.1031630000
_diffrn_orient_matrix_UB_33      -0.0329526000
_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  0.0342
_diffrn_reflns_av_unetI/netI     0.0220
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            20646
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.497
_diffrn_reflns_theta_min         4.305
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           '1 mA'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           '50 kV'
_exptl_absorpt_coefficient_mu    4.714
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.891
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.98a (Rigaku Oxford Diffraction, 2023) 
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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.572
_exptl_crystal_description       block
_exptl_crystal_F_000             828
_exptl_crystal_size_max          0.106
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.022
_refine_diff_density_max         0.471
_refine_diff_density_min         -0.545
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     208
_refine_ls_number_reflns         3452
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0273
_refine_ls_R_factor_gt           0.0258
_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^)+(0.0322P)^2^+1.2268P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0676
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3259
_reflns_number_total             3452
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj04085j2.cif
_cod_data_source_block           ksgy33
_cod_database_code               7064209
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         CHNSCuClO
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.635
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B),
 C17(H17A,H17B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C12(H12)
;
_shelx_res_checksum              30392
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder'
_olex2_submission_original_sample_id KSB_240528_SDc_KSGY33
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.260
_oxdiff_exptl_absorpt_empirical_full_min 0.809