Impact of ligand steric hindrance on the phenoxazinone synthase-like reactivity and antibacterial activity of cobalt(iii) complexes of N2O donor ligands
Vidya, Kannan Sree; Yamuna, Ganesh; Bhuvanesh, Nattamai; Ghosh, Ayyan; Dasgupta, Sreeja; Mandal, Sukanta; Vasanthkumar, Rajkumar; Gurusaravanan, Packiaraj; Sundaravel, Karuppasamy; New Journal of Chemistry 49 (2025) 8576–8593; doi:10.1039/D5NJ00515A

data_7063881
_publ_section_title
;
 Impact of ligand steric hindrance on the phenoxazinone synthase-like
 reactivity and antibacterial activity of cobalt(iii) complexes of N2O
 donor ligands
;
_journal_issue                   20
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              8576
_journal_page_last               8593
_journal_paper_doi               10.1039/D5NJ00515A
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C18 H27 Co N4 O2, 1.92(H2 O), 2(N O3)'
_chemical_formula_sum            'C18 H30.84 Co N6 O9.92'
_chemical_formula_weight         548.97
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-07
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-02-03 deposited with the CCDC.	2025-04-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.425(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.3873(4)
_cell_length_b                   20.8399(6)
_cell_length_c                   15.6429(4)
_cell_measurement_reflns_used    23318
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.8900
_cell_measurement_theta_min      3.5430
_cell_volume                     4626.9(2)
_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 0.997
_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   -119.00 -29.00   0.50    0.50    --  -47.47 -65.00-147.00  180
  2  \w    -65.00  25.00   0.50    0.50    --  -47.47  65.00 -11.00  180
  3  \w    -65.00  25.00   0.50    0.50    --  -47.47  65.00 -11.00  180
  4  \w    -24.00  65.00   0.50    0.50    --   47.47 -65.00-147.00  178
  5  \w    -83.00 -19.00   0.50    6.00    --  -91.75  65.00 -11.00  128
  6  \w   -163.00 -74.00   0.50    6.00    --  -91.75 -65.00-147.00  178
  7  \w     95.00 178.00   0.50    6.00    --  113.25  65.00 -11.00  166
  8  \w     42.00  83.00   0.50    6.00    --  113.25 -65.00-147.00   82
  9  \w    -13.00  28.00   0.50    0.50    --  -47.47  19.00   0.00   82
 10  \w    -39.00  26.00   0.50    0.50    --  -47.47  38.00-180.00  130
 11  \w    -13.00  28.00   0.50    0.50    --  -47.47  19.00 120.00   82
 12  \w     51.00  76.00   0.50    0.50    --   47.47  65.00 -11.00   50
 13  \w    -27.00  11.00   0.50    0.50    --   47.47 -19.00  60.00   76
 14  \w    -49.00 -24.00   0.50    6.00    --  -91.75  45.00 150.00   50
 15  \w    -49.00 -24.00   0.50    6.00    --  -91.75  45.00-180.00   50
 16  \w     44.00  70.00   0.50    6.00    --  113.25 -61.00  90.00   52
 17  \w     42.00  74.00   0.50    6.00    --  113.25 -61.00 -60.00   64
 18  \w     42.00  72.00   0.50    6.00    --  113.25 -61.00   0.00   60
 19  \w     50.00  86.00   0.50    6.00    --  113.25-125.00  90.00   72
 20  \w    113.00 138.00   0.50    6.00    --  113.25  77.00-150.00   50
 21  \w    141.00 173.00   0.50    6.00    --  113.25  77.00-150.00   64
 22  \w    102.00 142.00   0.50    6.00    --  113.25  45.00 120.00   80
 23  \w    136.00 177.00   0.50    6.00    --  113.25  30.00 120.00   82
 24  \w    101.00 176.00   0.50    6.00    --  113.25  30.00 -60.00  150
 25  \w     44.00  72.00   0.50    6.00    --  113.25 -61.00 120.00   56
 26  \w     74.00 109.00   0.50    6.00    --  113.25-125.00   0.00   70
 27  \w     48.00  90.00   0.50    6.00    --  113.25 -95.00  90.00   84
 28  \w    102.00 133.00   0.50    6.00    --  113.25  30.00 120.00   62
 29  \w     43.00  73.00   0.50    6.00    --  113.25 -61.00 -90.00   60
 30  \w    109.00 171.00   0.50    6.00    --  113.25  61.00  30.00  124
 31  \w    150.00 176.00   0.50    6.00    --  113.25  45.00 120.00   52
 32  \w     52.00  83.00   0.50    6.00    --  113.25 -95.00 -90.00   62
 33  \w     44.00  74.00   0.50    6.00    --  113.25 -61.00 150.00   60
 34  \w    112.00 155.00   0.50    6.00    --  113.25  30.00 -90.00   86
;
_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      -0.0860224000
_diffrn_orient_matrix_UB_12      -0.0103626000
_diffrn_orient_matrix_UB_13      -0.0713488000
_diffrn_orient_matrix_UB_21      -0.0525730000
_diffrn_orient_matrix_UB_22      0.0541367000
_diffrn_orient_matrix_UB_23      0.0390938000
_diffrn_orient_matrix_UB_31      0.0397840000
_diffrn_orient_matrix_UB_32      0.0493376000
_diffrn_orient_matrix_UB_33      -0.0579971000
_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  0.0495
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            46750
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.500
_diffrn_reflns_theta_min         3.564
_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    6.413
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.219
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.576
_exptl_crystal_description       plate
_exptl_crystal_F_000             2298
_exptl_crystal_size_max          0.372
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.046
_refine_diff_density_max         1.005
_refine_diff_density_min         -0.861
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     696
_refine_ls_number_reflns         9428
_refine_ls_number_restraints     254
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.0622
_refine_ls_R_factor_gt           0.0573
_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^)+(0.0931P)^2^+5.1330P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1559
_refine_ls_wR_factor_ref         0.1596
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8485
_reflns_number_total             9428
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00515a2.cif
_cod_data_source_block           kssv46
_cod_database_code               7063881
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         'C144  H235  Co8  N48  O80'
_chemical_oxdiff_usercomment     'Broken from larger crystal'
_shelx_estimated_absorpt_t_max   0.757
_shelx_estimated_absorpt_t_min   0.199
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 O2M-O3M \\sim O3M-O4M \\sim O4M-O2M
 with sigma of 0.04
 N1M-O2M \\sim N1M-O3M \\sim N1M-O4M
 with sigma of 0.02
 O14M-O15M \\sim O15M-O16M \\sim O16M-O14M
 with sigma of 0.04
 N13M-O14M \\sim N13M-O15M \\sim N13M-O16M
 with sigma of 0.02
 O2N-O3N \\sim O3N-O4N \\sim O4N-O2N
 with sigma of 0.01
 N1N-O2N \\sim N1N-O3N \\sim N1N-O4N
 with sigma of 0.01
3. Restrained planarity
 O2M, O3M, O4M, N1M
 with sigma of 0.1
 O14M, O15M, O16M, N13M
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O2M \\sim O3M \\sim O4M \\sim N1M: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
O2N \\sim O3N \\sim O4N \\sim N1N \\sim O2M \\sim O3M \\sim O4M \\sim N1M:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O14M \\sim O15M \\sim O16M \\sim N13M: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O14N \\sim O15N \\sim O16N \\sim N13N \\sim O14M \\sim O15M \\sim O16M \\sim
N13M: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
Uanis(O2M) = Uanis(O2N)
Uanis(N13M) = Uanis(N13N)
5. Rigid body (RIGU) restrains
 O2M, O3M, O4M, N1M
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2N, O3N, O4N, N1N, O2M, O3M, O4M, N1M
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O14M, O15M, O16M, N13M
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O14N, O15N, O16N, N13N, O14M, O15M, O16M, N13M
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Sof(N1M)=Sof(O2M)=Sof(O3M)=Sof(O4M)=Sof(O1V)=Sof(H1VA)=Sof(H1VB)=1-FVAR(1)
 Sof(O1W)=Sof(H1WA)=Sof(H1WB)=Sof(O2N)=Sof(O3N)=Sof(O4N)=Sof(N1N)=FVAR(1)
 Sof(N13M)=Sof(O14M)=Sof(O15M)=Sof(O16M)=1-FVAR(2)
 Sof(O14N)=Sof(O15N)=Sof(O16N)=Sof(N13N)=FVAR(2)
 Fixed Sof: O4W(0.84) H4WA(0.84) H4WB(0.84)
7.a Riding coordinates:
 O2(H2), O2B(H2BA), O2W(H2WA,H2WB), O3W(H3WA,H3WB), O4W(H4WA,H4WB), O1W(H1WA,
 H1WB), O1V(H1VA,H1VB)
7.b Free rotating group:
 N1M(O2M,O3M,O4M), N13M(O14M,O15M,O16M)
7.c Ternary CH refined with riding coordinates:
 N2(H2A), N3(H3), C8(H8), C17(H17), N2B(H2BB), N3B(H3B), C8B(H8B), C17B(H17B)
7.d Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C15(H15A,H15B), C16(H16A,H16B), C6B(H6BA,H6BB),
 C7B(H7BA,H7BB), C15B(H15C,H15D), C16B(H16C,H16D)
7.e Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2B), C3(H3A), C4(H4), C10(H10), C11(H11), C12(H12), C13(H13),
 C1B(H1B), C2B(H2BC), C3B(H3BA), C4B(H4B), C10B(H10B), C11B(H11B), C12B(H12B),
 C13B(H13B)
7.f Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C18(H18A,H18B,H18C), C9B(H9BA,H9BB,H9BC), C18B(H18D,H18E,H18F)
;
_shelx_res_checksum              84669
_shelx_hkl_checksum              69410
_olex2_submission_original_sample_id KSB_240416_SDc_KSSV46
_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 1.535
_oxdiff_exptl_absorpt_empirical_full_min 0.791