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_7064207
_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         'C15 H17 Cl2 Cu N3, 0.5(H2 O)'
_chemical_formula_sum            'C15 H18 Cl2 Cu N3 O0.5'
_chemical_formula_weight         382.76
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_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                97.283(2)
_cell_angle_beta                 102.476(2)
_cell_angle_gamma                90.793(2)
_cell_formula_units_Z            4
_cell_length_a                   8.6151(2)
_cell_length_b                   13.3450(2)
_cell_length_c                   14.5030(3)
_cell_measurement_reflns_used    31242
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.1970
_cell_measurement_theta_min      4.2600
_cell_volume                     1613.42(6)
_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  (Sheldrick, 2015)'
_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 0.993
_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     11.00  37.00   0.50    0.05    --   26.00  58.00 175.89   52
  2  \w     16.00  46.00   0.50    0.05    --   30.00  53.00  43.52   60
  3  \w     16.00  42.00   0.50    0.05    --   30.00  55.00   3.55   52
  4  \w     16.00  48.00   0.50    0.05    --   30.00  52.00  74.95   64
  5  \w      5.00  31.00   0.50    0.05    --   22.00  62.00 -40.61   52
  6  \w     20.00  46.00   0.50    0.05    --   34.00  53.00-119.95   52
  7  \w     -1.00  25.00   0.50    0.05    --   18.00  67.00-160.32   52
  8  \w     43.00  94.00   0.50    0.20    --  113.25 -95.00  30.00  102
  9  \w     44.00 108.00   0.50    0.20    --  113.25-108.00 107.00  128
 10  \w     21.00  85.00   0.50    0.05    --   48.16-108.00 107.00  128
 11  \w     46.00  74.00   0.50    0.20    --  113.25 -95.00   0.00   56
 12  \w     77.00 105.00   0.50    0.20    --  113.25 -95.00   0.00   56
 13  \w     44.00  98.00   0.50    0.20    --  113.25-125.00 -60.00  108
 14  \w     42.00  73.00   0.50    0.20    --  113.25 -95.00 -60.00   62
 15  \w     44.00  78.00   0.50    0.20    --  113.25-125.00-120.00   68
 16  \w     79.00 106.00   0.50    0.20    --  113.25 -95.00-180.00   54
 17  \w     34.00  94.00   0.50    0.05    --   48.16-125.00-150.00  120
 18  \w     48.00 104.00   0.50    0.20    --  113.25 -95.00  60.00  112
 19  \w     43.00 105.00   0.50    0.20    --  113.25 -95.00 120.00  124
 20  \w     75.00 105.00   0.50    0.20    --  113.25 -95.00 150.00   60
 21  \w     42.00  67.00   0.50    0.20    --  113.25 -95.00 150.00   50
 22  \w     81.00 106.00   0.50    0.20    --  113.25 -95.00 -60.00   50
 23  \w     79.00 105.00   0.50    0.20    --  113.25 -95.00 -90.00   52
 24  \w     42.00 106.00   0.50    0.20    --  113.25 -95.00-120.00  128
 25  \w     42.00  76.00   0.50    0.20    --  113.25 -95.00-180.00   68
 26  \w    -23.00  63.00   0.50    0.05    --   48.16 -57.00-180.00  172
 27  \w     42.00  67.00   0.50    0.20    --  113.25 -61.00 -60.00   50
 28  \w     46.00  71.00   0.50    0.20    --  113.25 -61.00 120.00   50
 29  \w    106.00 178.00   0.50    0.20    --  113.25  61.00  30.00  144
 30  \w    114.00 174.00   0.50    0.20    --  113.25  77.00  60.00  120
 31  \w    106.00 157.00   0.50    0.20    --  113.25  61.00 120.00  102
 32  \w    107.00 178.00   0.50    0.20    --  113.25  61.00 150.00  142
 33  \w    143.00 169.00   0.50    0.20    --  113.25  61.00 -30.00   52
 34  \w    147.00 173.00   0.50    0.20    --  113.25  61.00 -90.00   52
 35  \w    108.00 178.00   0.50    0.20    --  113.25  61.00-120.00  140
 36  \w    109.00 140.00   0.50    0.20    --  113.25  61.00 -90.00   62
 37  \w    106.00 177.00   0.50    0.20    --  113.25  61.00-180.00  142
 38  \w    109.00 139.00   0.50    0.20    --  113.25  61.00 -60.00   60
 39  \w    104.00 152.00   0.50    0.20    --  113.25  45.00-150.00   96
 40  \w    102.00 129.00   0.50    0.20    --  113.25  45.00 -60.00   54
 41  \w    102.00 128.00   0.50    0.20    --  113.25  45.00-180.00   52
 42  \w    106.00 136.00   0.50    0.20    --  113.25  61.00 -30.00   60
 43  \w    142.00 168.00   0.50    0.20    --  113.25  45.00 -90.00   52
 44  \w    103.00 136.00   0.50    0.20    --  113.25  45.00 -90.00   66
 45  \w    136.00 178.00   0.50    0.20    --  113.25  45.00 -60.00   84
 46  \w    106.00 164.00   0.50    0.20    --  113.25  61.00  90.00  116
 47  \w    146.00 178.00   0.50    0.20    --  113.25  45.00 120.00   64
 48  \w    103.00 129.00   0.50    0.20    --  113.25  45.00 150.00   52
 49  \w    106.00 139.00   0.50    0.20    --  113.25  45.00 120.00   66
 50  \w    141.00 178.00   0.50    0.20    --  113.25  45.00  60.00   74
 51  \w    107.00 135.00   0.50    0.20    --  113.25  45.00  60.00   56
 52  \w    101.00 156.00   0.50    0.20    --  113.25  45.00  30.00  110
 53  \w    101.00 147.00   0.50    0.20    --  113.25  45.00  90.00   92
 54  \w    102.00 154.00   0.50    0.20    --  113.25  45.00   0.00  104
 55  \w    148.00 177.00   0.50    0.20    --  113.25  45.00-120.00   58
 56  \w    146.00 171.00   0.50    0.20    --  113.25  45.00-180.00   50
 57  \w    102.00 130.00   0.50    0.20    --  113.25  45.00-120.00   56
 58  \w    120.00 175.00   0.50    0.20    --  113.25  15.00   0.00  110
 59  \w    109.00 158.00   0.50    0.20    --  113.25  30.00  90.00   98
 60  \w    111.00 166.00   0.50    0.20    --  113.25 125.00 120.00  110
 61  \w    118.00 158.00   0.50    0.20    --  113.25 125.00  60.00   80
 62  \w    119.00 165.00   0.50    0.20    --  113.25 125.00 -30.00   92
 63  \w    104.00 178.00   0.50    0.20    --  113.25 108.00-155.00  148
 64  \w    115.00 164.00   0.50    0.20    --  113.25 125.00-180.00   98
 65  \w    -15.00  11.00   0.50    0.05    --   10.00  83.00  98.76   52
 66  \w    -39.00  25.00   0.50    0.05    --  -48.16  38.00   0.00  128
 67  \w    -82.00 -22.00   0.50    0.20    --  -91.75 108.00-155.00  120
 68  \w    -81.00   0.00   0.50    0.05    --  -48.16 108.00-155.00  162
 69  \w    -54.00 -28.00   0.50    0.05    --  -42.00 -50.00-170.61   52
 70  \w    -61.00 -28.00   0.50    0.05    --  -42.00 -48.00-110.81   66
 71  \w    -54.00 -28.00   0.50    0.05    --  -42.00 -50.00 -23.50   52
 72  \w   -122.00 -37.00   0.50    0.05    --  -50.00 -45.00 -50.43  170
 73  \w   -122.00 -37.00   0.50    0.05    --  -50.00 -45.00  20.88  170
 74  \w    -54.00 -28.00   0.50    0.05    --  -42.00 -50.00  78.26   52
 75  \w    -54.00 -28.00   0.50    0.05    --  -42.00 -50.00 143.08   52
 76  \w   -134.00 -49.00   0.50    0.05    --  -62.00 -47.00 119.30  170
 77  \w   -138.00 -53.00   0.50    0.05    --  -66.00 -47.00 104.71  170
 78  \w   -142.00 -57.00   0.50    0.05    --  -70.00 -47.00  19.90  170
 79  \w   -142.00 -57.00   0.50    0.05    --  -70.00 -47.00  -5.75  170
 80  \w    -83.00 -57.00   0.50    0.05    --  -70.00 -47.00  -5.75   52
 81  \w   -138.00 -53.00   0.50    0.05    --  -66.00 -47.00 -81.50  170
 82  \w   -142.00 -57.00   0.50    0.05    --  -70.00 -47.00-152.64  170
 83  \w    -89.00 -57.00   0.50    0.05    --  -70.00 -47.00-115.88   64
 84  \w   -114.00 -88.00   0.50    0.20    --  -91.75 -47.00 -45.75   52
 85  \w   -110.00 -84.00   0.50    0.20    --  -91.75 -47.00 -77.94   52
 86  \w   -151.00-125.00   0.50    0.20    --  -91.75 -47.00 -45.75   52
 87  \w   -152.00-118.00   0.50    0.20    --  -91.75 -47.00 -77.94   68
 88  \w   -107.00 -81.00   0.50    0.20    --  -91.75 -47.00  29.51   52
 89  \w   -106.00 -81.00   0.50    0.20    --  -91.75 -47.00 -40.10   50
 90  \w   -138.00-112.00   0.50    0.05    --  -78.00 -46.00 -82.95   52
 91  \w   -133.00 -80.00   0.50    0.20    --  -91.75 -46.00-110.94  106
 92  \w   -111.00 -85.00   0.50    0.20    --  -91.75 -47.00 129.79   52
 93  \w   -116.00 -82.00   0.50    0.20    --  -91.75 -47.00 159.56   68
 94  \w   -106.00 -81.00   0.50    0.20    --  -91.75 -47.00 175.10   50
 95  \w   -125.00 -41.00   0.50    0.05    --  -54.00 -46.00 151.15  168
 96  \w   -138.00 -53.00   0.50    0.05    --  -66.00 -46.00 135.89  170
 97  \w   -107.00 -79.00   0.50    0.20    --  -91.75 -46.00  75.08   56
 98  \w   -138.00 -53.00   0.50    0.05    --  -66.00 -46.00  75.99  170
 99  \w   -134.00 -49.00   0.50    0.05    --  -62.00 -46.00  31.92  170
100  \w    -87.00 -61.00   0.50    0.05    --  -74.00 -46.00  31.58   52
101  \w   -118.00 -81.00   0.50    0.20    --  -91.75 -46.00 166.01   74
102  \w   -162.00-132.00   0.50    0.20    --  -91.75 -46.00 166.01   60
103  \w   -100.00 -73.00   0.50    0.20    --  -86.00 -45.00 132.75   54
104  \w    -88.00 -62.00   0.50    0.05    --  -74.00 -46.00 -29.15   52
105  \w    -90.00 -65.00   0.50    0.05    --  -78.00 -46.00 -82.95   50
106  \w   -134.00 -49.00   0.50    0.05    --  -62.00 -46.00-178.96  170
107  \w   -134.00 -49.00   0.50    0.05    --  -62.00 -46.00-178.96  170
108  \w   -120.00 -79.00   0.50    0.20    --  -91.75 -45.00-150.00   82
109  \w   -163.00-126.00   0.50    0.20    --  -91.75 -45.00  -7.45   74
110  \w   -105.00 -79.00   0.50    0.20    --  -91.75 -45.00  -7.45   52
111  \w   -107.00 -76.00   0.50    0.20    --  -90.00 -44.00 -19.29   62
112  \w   -107.00 -79.00   0.50    0.20    --  -91.75 -45.00  43.09   56
113  \w   -104.00 -79.00   0.50    0.20    --  -91.75 -45.00  90.00   50
114  \w   -126.00 -41.00   0.50    0.05    --  -54.00 -44.00  40.14  170
115  \w   -111.00 -76.00   0.50    0.20    --  -90.00 -43.00 179.24   70
116  \w   -102.00 -76.00   0.50    0.20    --  -90.00 -43.00  -0.43   52
117  \w    -97.00 -65.00   0.50    0.05    --  -78.00 -42.00 -49.78   64
118  \w   -103.00 -78.00   0.50    0.20    --  -91.75 -43.00 -79.96   50
119  \w   -106.00 -65.00   0.50    0.05    --  -78.00 -44.00-116.00   82
120  \w   -141.00-115.00   0.50    0.05    --  -78.00 -44.00-116.00   52
121  \w   -133.00 -76.00   0.50    0.20    --  -90.00 -43.00-137.37  114
122  \w   -103.00 -78.00   0.50    0.20    --  -90.00 -41.00 103.50   50
123  \w   -161.00 -82.00   0.50    0.20    --  -91.75-108.00 107.00  158
;
_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      0.0176752000
_diffrn_orient_matrix_UB_12      -0.0532323000
_diffrn_orient_matrix_UB_13      -0.0976116000
_diffrn_orient_matrix_UB_21      0.0345654000
_diffrn_orient_matrix_UB_22      -0.0994068000
_diffrn_orient_matrix_UB_23      0.0428358000
_diffrn_orient_matrix_UB_31      -0.1791564000
_diffrn_orient_matrix_UB_32      -0.0294529000
_diffrn_orient_matrix_UB_33      -0.0260918000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0144
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            7240
_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         74.615
_diffrn_reflns_theta_min         3.342
_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    4.954
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32476
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.98a (Rigaku Oxford Diffraction, 2023) 
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    1.576
_exptl_crystal_description       plank
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.64
_exptl_crystal_size_mid          0.047
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.606
_refine_diff_density_min         -0.586
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         7240
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0384
_refine_ls_R_factor_gt           0.0372
_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^)+(0.0795P)^2^+0.7686P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1102
_refine_ls_wR_factor_ref         0.1118
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6892
_reflns_number_total             7240
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9584\% 
around [0.94 -0.02 -0.34] (reciprocal) or [1.00 0.00 0.00] (direct)
;
_cod_data_source_file            d5nj04085j2.cif
_cod_data_source_block           ksgy32_twin1_hklf4
_cod_original_formula_sum        'C15 H18 Cl2 Cu N3 O0.50'
_cod_database_code               7064207
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         CHNSCuClO
_shelx_estimated_absorpt_t_max   0.823
_shelx_estimated_absorpt_t_min   0.144
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.669(2)
 0.331(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H,H) groups
3.a Free rotating group:
 O1W(H1WA,H1WB)
3.b Ternary CH refined with riding coordinates:
 C13B(H13B), C13(H13)
3.c Secondary CH2 refined with riding coordinates:
 C7B(H7BA,H7BB), C6B(H6BA,H6BB), C6(H6A,H6B), C7(H7A,H7B), C14(H14C,H14D),
 C14B(H14A,H14B), C15(H15C,H15D), C15B(H15A,H15B)
3.d Aromatic/amide H refined with riding coordinates:
 C12B(H12B), C4B(H4B), C1B(H1B), C10B(H10B), C11B(H11B), C12(H12), C2(H2),
 C9B(H9B), C2B(H2B), C1(H1), C3(H3), C4(H4), C3B(H3B), C10(H10), C11(H11),
 C9(H9)
;
_shelx_res_checksum              33364
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder'
_olex2_submission_original_sample_id KSB_240528_SDc_KSGY32
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.834
_oxdiff_exptl_absorpt_empirical_full_min 0.497
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2