Site specific redox properties in ligand differentiated di-nickel complexes inspired by the acetyl CoA synthase active site.
Quiroz, Manuel; Jana, Manish; Liu, Kaiyang; Bhuvanesh, Nattamai; Hall, Michael B.; Darensbourg, Marcetta Y.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 7414–7423; doi:10.1039/d4dt00306c

data_7715691
_publ_section_title
;
 Site specific redox properties in ligand differentiated di-nickel
 complexes inspired by the acetyl CoA synthase active site.
;
_journal_issue                   17
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7414
_journal_page_last               7423
_journal_paper_doi               10.1039/d4dt00306c
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C20 H18 N2 Ni2 O2 S4, 2(C8 H20 N)'
_chemical_formula_sum            'C36 H58 N4 Ni2 O2 S4'
_chemical_formula_weight         824.52
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-05-28
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-01-31 deposited with the CCDC.	2024-04-01 downloaded from the CCDC.
;
_cell_angle_alpha                83.934(2)
_cell_angle_beta                 70.9880(10)
_cell_angle_gamma                68.434(2)
_cell_formula_units_Z            4
_cell_length_a                   13.2528(5)
_cell_length_b                   16.1861(7)
_cell_length_c                   20.3139(8)
_cell_measurement_reflns_used    9998
_cell_measurement_temperature    110.0
_cell_measurement_theta_max      27.544
_cell_measurement_theta_min      2.325
_cell_volume                     3831.0(3)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL n/a (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker QUEST PHOTON-III'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0463
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            149361
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.568
_diffrn_reflns_theta_min         1.785
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.239
_exptl_absorpt_correction_T_max  0.3334
_exptl_absorpt_correction_T_min  0.2058
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1331 before and 0.0784 after correction.
The Ratio of minimum to maximum transmission is 0.6173.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.430
_exptl_crystal_description       block
_exptl_crystal_F_000             1752
_exptl_crystal_size_max          0.519
_exptl_crystal_size_mid          0.482
_exptl_crystal_size_min          0.322
_refine_diff_density_max         0.629
_refine_diff_density_min         -0.812
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     961
_refine_ls_number_reflns         17644
_refine_ls_number_restraints     595
_refine_ls_restrained_S_all      1.398
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0290
_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^)+(0.0298P)^2^+2.4539P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0682
_refine_ls_wR_factor_ref         0.0718
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14665
_reflns_number_total             17644
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00306c2.cif
_cod_data_source_block           nemanis2
_cod_depositor_comments
'Adding full bibliography for 7715688--7715691.cif.'
_cod_database_code               7715691
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.691
_shelx_estimated_absorpt_t_min   0.566
_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
2. Restrained distances
 N8-C71A \\sim N8-C71 \\sim N8-C69A \\sim N8-C69 \\sim N8-C67A \\sim N8-C67
\\sim N8-C65A \\sim N8-C65 ~
 N7-C57A \\sim N7-C57 \\sim N7-C63A \\sim N7-C63 \\sim N6-C53 \\sim N6-C53A
 with sigma of 0.01
 C72-C71 \\sim C72A-C71A \\sim C70A-C69A \\sim C70-C69 \\sim C68-C67 \\sim
C68A-C67A \\sim C66A-C65A ~
 C66-C65 \\sim C64A-C63A \\sim C64-C63 \\sim C58-C57 \\sim C54-C53 \\sim
C54A-C53A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
N8 \\sim C65A \\sim C66A \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71
\\sim C72 \\sim C65 \\sim C66 \\sim C67A \\sim C68A \\sim C69A \\sim C70A \\sim
C71A \\sim C72A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C57 \\sim C58 \\sim C57A \\sim C58A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C63 \\sim C64 \\sim C63A \\sim C64A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C53 \\sim C54 \\sim C53A \\sim C54A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C66A) = Uanis(C66)
Uanis(C71) = Uanis(C71A)
Uanis(C67A) = Uanis(C67)
Uanis(C65) = Uanis(C65A)
Uanis(N8) = Uanis(C65) = Uanis(C65A)
Uanis(C63) = Uanis(C63A)
Uanis(C64) = Uanis(C64A)
Uanis(C57A) = Uanis(C57)
Uanis(C53A) = Uanis(C53)
4. Rigid body (RIGU) restrains
 N8, C65A, C66A, C67, C68, C69, C70, C71, C72, C65, C66, C67A, C68A, C69A,
 C70A, C71A, C72A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C57, C58, C57A, C58A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C63, C64, C63A, C64A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C53, C54, C53A, C54A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C53A)=Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=1-FVAR(1)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(1)
 Fixed Sof: C57(0.5) H57A(0.5) H57B(0.5) C58(0.5) H58A(0.5) H58B(0.5)
 H58C(0.5) C57A(0.5) H57C(0.5) H57D(0.5) C58A(0.5) H58D(0.5) H58E(0.5)
 H58F(0.5) C63(0.5) H63A(0.5) H63B(0.5) C64(0.5) H64A(0.5) H64B(0.5) H64C(0.5)
 C63A(0.5) H63C(0.5) H63D(0.5) C64A(0.5) H64D(0.5) H64E(0.5) H64F(0.5)
 C65A(0.5) H65A(0.5) H65B(0.5) C66A(0.5) H66A(0.5) H66B(0.5) H66C(0.5) C67(0.5)
 H67A(0.5) H67B(0.5) C68(0.5) H68A(0.5) H68B(0.5) H68C(0.5) C69(0.5) H69A(0.5)
 H69B(0.5) C70(0.5) H70A(0.5) H70B(0.5) H70C(0.5) C71(0.5) H71A(0.5) H71B(0.5)
 C72(0.5) H72A(0.5) H72B(0.5) H72C(0.5) C65(0.5) H65C(0.5) H65D(0.5) C66(0.5)
 H66D(0.5) H66E(0.5) H66F(0.5) C67A(0.5) H67C(0.5) H67D(0.5) C68A(0.5)
 H68D(0.5) H68E(0.5) H68F(0.5) C69A(0.5) H69C(0.5) H69D(0.5) C70A(0.5)
 H70D(0.5) H70E(0.5) H70F(0.5) C71A(0.5) H71C(0.5) H71D(0.5) C72A(0.5)
 H72D(0.5) H72E(0.5) H72F(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C4(H4A,H4B), C6(H6A,H6B), C21(H21A,H21B), C23(H23A,
 H23B), C24(H24A,H24B), C26(H26A,H26B), C41(H41A,H41B), C43(H43A,H43B),
 C45(H45A,H45B), C47(H47A,H47B), C49(H49A,H49B), C51(H51A,H51B), C53(H53A,H53B),
  C53A(H53C,H53D), C55(H55A,H55B), C57(H57A,H57B), C57A(H57C,H57D), C59(H59A,
 H59B), C61(H61A,H61B), C63(H63A,H63B), C63A(H63C,H63D), C65A(H65A,H65B),
 C67(H67A,H67B), C69(H69A,H69B), C71(H71A,H71B), C65(H65C,H65D), C67A(H67C,
 H67D), C69A(H69C,H69D), C71A(H71C,H71D)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34),
  C36(H36), C37(H37), C38(H38), C39(H39), C40(H40)
6.c Idealised Me refined as rotating group:
 C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C48(H48A,H48B,
 H48C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C),
 C54A(H54D,H54E,H54F), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C58A(H58D,H58E,
 H58F), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C64(H64A,H64B,H64C),
 C64A(H64D,H64E,H64F), C66A(H66A,H66B,H66C), C68(H68A,H68B,H68C), C70(H70A,H70B,
 H70C), C72(H72A,H72B,H72C), C66(H66D,H66E,H66F), C68A(H68D,H68E,H68F),
 C70A(H70D,H70E,H70F), C72A(H72D,H72E,H72F)
;
_shelx_res_checksum              32816
_olex2_submission_special_instructions 'No special instructions were received'