A tetranuclear Mn-diamond core complex as a functional mimic of both catechol oxidase and phenoxazinone synthase enzymes
Kumar, Rakesh; Keshri, Rahul; Prodhan, Koushik; Shaikh, Kanchan; Draksharapu, Apparao; Dalton Transactions  (2023) –; doi:10.1039/D3DT00761H

data_7713010
_publ_section_title
;
 A tetranuclear Mn-diamond core complex as a functional mimic of both
 catechol oxidase and phenoxazinone synthase enzymes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00761H
_journal_year                    2023
_chemical_formula_moiety         'C78 H111 Cl4 Mn4 N12 O32'
_chemical_formula_sum            'C78 H111 Cl4 Mn4 N12 O32'
_chemical_formula_weight         2090.34
_chemical_name_systematic        Mn-tetramer
_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
_audit_creation_date             2023-04-25
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-07 deposited with the CCDC.	2023-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                95.953(2)
_cell_angle_beta                 93.623(2)
_cell_angle_gamma                108.608(2)
_cell_formula_units_Z            1
_cell_length_a                   11.6386(11)
_cell_length_b                   14.8042(14)
_cell_length_c                   16.7878(16)
_cell_measurement_reflns_used    9905
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.22
_cell_measurement_theta_min      2.30
_cell_volume                     2712.3(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD 1K area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 1K area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0528
_diffrn_reflns_av_unetI/netI     0.0571
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            38201
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.047
_diffrn_reflns_theta_max         25.047
_diffrn_reflns_theta_min         2.303
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_target            Mo
_exptl_absorpt_coefficient_mu    0.628
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6571
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.'
_exptl_crystal_colour            'metallic dark green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             1087
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.144
_refine_diff_density_min         -1.449
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     616
_refine_ls_number_reflns         9595
_refine_ls_number_restraints     155
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.1172
_refine_ls_R_factor_gt           0.0826
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1084P)^2^+9.0664P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2078
_refine_ls_wR_factor_ref         0.2406
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6520
_reflns_number_total             9595
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00761h2.cif
_cod_data_source_block           17aprd_0m_b_sq
_cod_database_code               7713010
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.895
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 O3B-C26B
 1.6 with sigma of 0.02
 O3A-C26A
 1.6 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C14 \\sim C13 \\sim C12 \\sim C11 \\sim N2 \\sim C15: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 1.7A
O2: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
1.7A
O4: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
1.7A
C22B \\sim C23B \\sim C24B \\sim N3 \\sim C20 \\sim C21B: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
O8: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
1.7A
Uanis(O4) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O3B) = Uanis(C22B)
Uanis(C26B) = Uanis(O3B) = Uanis(C22B) = Uanis(C23B) = Uanis(C21B)
Uanis(C22B) = Uanis(C22A)
Uanis(C23B) = Uanis(C23A)
Uanis(C8A) = Uanis(C8B) = Uanis(O1B) = Uanis(O1A)
Uanis(C34) = Uanis(C32) = Uanis(C31) = Uanis(O4) = Uanis(C35)
4. Rigid body (RIGU) restrains
 C19, N6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13, C12, C11, N2, C15, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C24B, N3, C20, C21B, C22B, C23B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C24B(0.4) H24B(0.4) C23B(0.5) C22B(0.5) C21B(0.5) C27B(0.5)
 H27A(0.5) H27B(0.5) H27C(0.5) O3B(0.5) C25B(0.5) H25A(0.5) H25B(0.5) H25C(0.5)
 C26B(0.5) H26A(0.5) H26B(0.5) H26C(0.5) H1(0.4) O1B(0.5) O3A(0.5) C26A(0.5)
 H26D(0.5) H26E(0.5) H26F(0.5) C23A(0.5) C25A(0.5) H25D(0.5) H25E(0.5)
 H25F(0.5) C27A(0.5) H27D(0.5) H27E(0.5) H27F(0.5) C22A(0.5) C24A(0.6)
 H24A(0.6) C21A(0.5) O15B(0.7) O16A(0.5) O15A(0.5) O14B(0.5) O14A(0.5)
 O16B(0.5) O13B(0.5) O13A(0.3) O1A(0.5) C8B(0.5) H8BA(0.5) H8BB(0.5) H8BC(0.5)
 C8A(0.5) H8AA(0.5) H8AB(0.5) H8AC(0.5)
6.a Rotating group:
 O7(H7A,H7B), O8(H8A,H8B)
6.b Ternary CH refined with riding coordinates:
 C38(H38)
6.c Secondary CH2 refined with riding coordinates:
 C37(H37A,H37B), C39(H39A,H39B), C6(H6A,H6B), C19(H19A,H19B), C10(H10A,H10B),
 C28(H28A,H28B)
6.d Aromatic/amide H refined with riding coordinates:
 C33(H33), C15(H15), C24B(H24B), C1(H1), C24A(H24A)
6.e Fitted hexagon refined as free rotating group:
 C29(C30,C31,C32,C33,N4), C15(C14,C13,C12,C11,N2), N3(C24B,C23B,C22B,C21B,C20)
6.f Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C16(H16A,H16B,H16C), C36(H36A,H36B,H36C), C34(H34A,H34B,
 H34C), C27B(H27A,H27B,H27C), C25B(H25A,H25B,H25C), C26B(H26A,H26B,H26C),
 C9(H9A,H9B,H9C), C26A(H26D,H26E,H26F), C25A(H25D,H25E,H25F), C27A(H27D,H27E,
 H27F), C35(H35A,H35B,H35C), C17(H17A,H17B,H17C), C7(H7C,H7D,H7E), C8B(H8BA,
 H8BB,H8BC), C8A(H8AA,H8AB,H8AC)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 155 electrons were 
found in a volume of 520\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[C2H3N], 2[CH4O], 2[C4H10O] per Asymmetric Unit 
which account for 164 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              80428
_shelx_fab_checksum              26688
_olex2_submission_special_instructions 'No special instructions were received'