Direct O<sub>2</sub> mediated oxidation of a Ni(II)N<sub>3</sub>O structural model complex for the active site of nickel acireductone dioxygenase (Ni-ARD): characterization, biomimetic reactivity, and enzymatic implications.
Kirsch, Kelsey E.; Little, Mary E.; Cundari, Thomas R.; El-Shaer, Emily; Barone, Georgia; Lynch, Vincent M.; Toledo, Santiago A.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 17852–17863; doi:10.1039/d4dt02538e

data_7717208
_publ_section_title
;
 Direct O<sub>2</sub> mediated oxidation of a Ni(II)N<sub>3</sub>O
 structural model complex for the active site of nickel acireductone
 dioxygenase (Ni-ARD): characterization, biomimetic reactivity, and
 enzymatic implications.
;
_journal_issue                   44
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              17852
_journal_page_last               17863
_journal_paper_doi               10.1039/d4dt02538e
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C29 H35 F3 N3 Ni O6 S, C H2 Cl2'
_chemical_formula_sum            'C30 H37 Cl2 F3 N3 Ni O6 S'
_chemical_formula_weight         754.29
_chemical_name_common            'Ni(II)N3O OPhtbu NPyH Benzoic acid_OTf'
_chemical_name_systematic
'[NiII (N-(ethyl-N?Me2)(Py)(2-t-ButPhOH)(BenzoicAc)(OTf)]'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Hygroscopic,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yc'
_space_group_name_H-M_alt        'P 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-03
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-08-05 deposited with the CCDC.	2024-10-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.252(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.2655(3)
_cell_length_b                   11.9834(2)
_cell_length_c                   16.9887(3)
_cell_measurement_reflns_used    17953
_cell_measurement_temperature    100.0(6)
_cell_measurement_theta_max      75.5710
_cell_measurement_theta_min      2.7170
_cell_volume                     3338.11(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Shelxtl-Plus/XP, Bruker AXS, Inc. 2009'
_computing_publication_material  'Shelxtl-Plus, Bruker AXS, Inc. 2009'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(6)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.948
_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    -94.00 -12.00   0.50    3.00    --  -48.29 124.00 125.00  164
  2  \w     12.00  94.00   0.50    3.00    --   48.29-124.00  46.00  164
  3  \w     74.00 120.00   0.50    3.00    --   48.29 124.00 125.00   92
  4  \w     57.00 120.00   0.50    3.00    --   48.29 149.00 -70.00  126
  5  \w     26.00 109.00   0.50    3.00    --   48.29-149.00-117.00  166
  6  \w   -150.00 -75.00   0.50   11.00    -- -104.52-124.00  46.00  150
  7  \w    -95.00 -70.00   0.50   11.00    -- -104.52 124.00 125.00   50
  8  \w   -129.00 -77.00   0.50   11.00    -- -104.52 149.00 -70.00  104
  9  \w     75.00 140.00   0.50   11.00    --  104.52 124.00 125.00  130
 10  \w     47.00  72.00   0.50   11.00    --  104.52-124.00  46.00   50
 11  \w     59.00 129.00   0.50   11.00    --  104.52-149.00-117.00  140
 12  \w   -119.00 -82.00   0.50    3.00    --  -48.29 -57.00 -90.00   74
 13  \w   -118.00 -85.00   0.50    3.00    --  -48.29 -57.00 120.00   66
 14  \w     82.00 120.00   0.50    3.00    --   48.29  57.00 150.00   76
 15  \w   -176.00-102.00   0.50   11.00    -- -104.52-125.00 120.00  148
 16  \w   -177.00-101.00   0.50   11.00    -- -104.52 -77.00  60.00  152
 17  \w   -111.00 -32.00   0.50   11.00    -- -104.52  77.00 -30.00  158
 18  \w    -74.00 -33.00   0.50   11.00    -- -104.52  61.00 -30.00   82
 19  \w   -176.00-100.00   0.50   11.00    -- -104.52 -77.00 150.00  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0671724000
_diffrn_orient_matrix_UB_12      -0.0086995000
_diffrn_orient_matrix_UB_13      0.0417035000
_diffrn_orient_matrix_UB_21      0.0100103000
_diffrn_orient_matrix_UB_22      -0.1278116000
_diffrn_orient_matrix_UB_23      0.0045132000
_diffrn_orient_matrix_UB_31      0.0649515000
_diffrn_orient_matrix_UB_32      0.0110053000
_diffrn_orient_matrix_UB_33      0.0857572000
_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  0.0277
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.948
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            25771
_diffrn_reflns_point_group_measured_fraction_full 0.646
_diffrn_reflns_point_group_measured_fraction_max 0.618
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.269
_diffrn_reflns_theta_min         2.695
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.447
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.641
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.501
_exptl_crystal_description       prism
_exptl_crystal_F_000             1564
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.216
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.682
_refine_diff_density_min         -0.879
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.44(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     932
_refine_ls_number_reflns         8632
_refine_ls_number_restraints     669
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0533
_refine_ls_R_factor_gt           0.0520
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1070P)^2^+1.9703P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1460
_refine_ls_wR_factor_ref         0.1477
_reflns_Friedel_coverage         0.301
_reflns_Friedel_fraction_full    0.301
_reflns_Friedel_fraction_max     0.286
_reflns_number_gt                8319
_reflns_number_total             8632
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02538e2.cif
_cod_data_source_block           2hap-nin3o_auto
_cod_depositor_comments
'Adding full bibliography for 7717208--7717210.cif.'
_cod_database_code               7717208
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H37 N3 O6 F3 S Cl2 Ni'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.56(3)
 0.44(3)
2. 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
3. Restrained distances
 S3-C62
 1.85 with sigma of 0.03
 S2A-O11A
 1.44 with sigma of 0.03
 F7-F8
 2.23 with sigma of 0.02
 S2A-C61
 1.86 with sigma of 0.02
 S2-O11
 1.44 with sigma of 0.03
 F9-C61
 1.35 with sigma of 0.02
 F7-F9
 2.23 with sigma of 0.02
 F9-F8
 2.23 with sigma of 0.02
 F8-C61
 1.35 with sigma of 0.02
 F7-C61
 1.35 with sigma of 0.02
 S2A-O12A
 1.44 with sigma of 0.03
 S2-O12
 1.44 with sigma of 0.03
 F13-C62
 1.34 with sigma of 0.03
 F10-C62
 1.34 with sigma of 0.03
 F16-C62
 1.34 with sigma of 0.03
 F13-F10
 2.23 with sigma of 0.03
 F10-F16
 2.23 with sigma of 0.03
 F16-F13
 2.23 with sigma of 0.03
 O6A-S3
 1.44 with sigma of 0.03
4. Uiso/Uaniso restraints and constraints
F8 \\sim F6 \\sim F4 \\sim F5 \\sim F7 \\sim F9: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
F16 \\sim F10 \\sim F13: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(O11) = Uanis(O11A)
Uanis(F6) = Uanis(F8)
Uanis(F5) = Uanis(F7)
Uanis(O5) = Uanis(F16)
Uanis(F13) = Uanis(F1)
Uanis(O6A) = Uanis(O6)
5. Others
 Sof(S2A)=Sof(F9)=Sof(F7)=Sof(F8)=Sof(C61)=Sof(O12A)=Sof(O11A)=1-FVAR(1)
 Sof(S2)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(O11)=Sof(O12)=Sof(C58)=FVAR(1)
 Sof(S3)=Sof(F10)=Sof(C62)=Sof(F13)=Sof(F16)=Sof(O16)=Sof(O6A)=1-FVAR(2)
 Sof(S1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(O5)=Sof(O6)=Sof(C29)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C7(H7A,H7B), C14(H14A,H14B), C15(H15A,H15B), C35(H35A,H35B),
 C36(H36A,H36B), C43(H43A,H43B), C44(H44A,H44B), C59(H59A,H59B), C60(H60A,H60B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C11(H11), C12(H12), C13(H13), C24(H24),
 C25(H25), C26(H26), C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33),
  C40(H40), C41(H41), C42(H42), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57)
6.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C)
;
_shelx_res_checksum              35844
_shelx_hkl_checksum              53555
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.266
_oxdiff_exptl_absorpt_empirical_full_min 0.844