Cluster dynamics of heterometallic trinuclear clusters during ligand substitution, redox chemistry, and group transfer processes.
Juda, Cristin E.; Handford, Rex C.; Bartholomew, Amymarie K.; Powers, Tamara M.; Gu, Nina X.; Meyer, Elisabeth; Roth, Nikolaj; Chen, Yu-Sheng; Zheng, Shao-Liang; Betley, Theodore A.; Chemical science 15 (2024) 8242–8248; doi:10.1039/d3sc03606e

data_1571015
_publ_section_title
;
 Cluster dynamics of heterometallic trinuclear clusters during ligand
 substitution, redox chemistry, and group transfer processes.
;
_journal_issue                   21
_journal_name_full               'Chemical science'
_journal_page_first              8242
_journal_page_last               8248
_journal_paper_doi               10.1039/d3sc03606e
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety
'C50 H69 F6 Fe2.07 N7 Si3 Zn0.93, C18 H36 K N2 O6, 2.63(C4 H10 O)'
_chemical_formula_sum            'C78.5 H131.25 F6 Fe2.1 K N9 O8.62 Si3 Zn0.9'
_chemical_formula_weight         1752.63
_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
_audit_creation_date             2017-09-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2020-03-27 deposited with the CCDC.	2024-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                78.4010(10)
_cell_angle_beta                 74.3150(10)
_cell_angle_gamma                83.1370(10)
_cell_formula_units_Z            4
_cell_length_a                   15.4746(7)
_cell_length_b                   23.8238(11)
_cell_length_c                   27.1431(13)
_cell_measurement_reflns_used    9839
_cell_measurement_temperature    100
_cell_measurement_theta_max      14.761
_cell_measurement_theta_min      2.203
_cell_volume                     9414.8(8)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'APEX3 v2016.1.0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT-2014 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device_type
;
Bruker D8 goniometer with CCD area detector
;
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.41328
_diffrn_reflns_av_R_equivalents  0.1245
_diffrn_reflns_av_unetI/netI     0.0563
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            479481
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        14.357
_diffrn_reflns_theta_max         14.987
_diffrn_reflns_theta_min         1.040
_diffrn_source                   synchrotron
_exptl_absorpt_coefficient_mu    0.508
_exptl_absorpt_correction_T_max  1.0136
_exptl_absorpt_correction_T_min  0.9094
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1852 before and 0.0751 after correction.
The Ratio of minimum to maximum transmission is 0.8972.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_density_diffrn    1.236
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             3723
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.163
_refine_diff_density_min         -0.799
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2096
_refine_ls_number_reflns         37723
_refine_ls_number_restraints     365
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0838
_refine_ls_R_factor_gt           0.0548
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0663P)^2^+14.8231P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1373
_refine_ls_wR_factor_ref         0.1538
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27581
_reflns_number_total             37723
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03606e2.cif
_cod_data_source_block           zsl_CCDC1
_cod_depositor_comments
'Adding full bibliography for 1571003--1571015.cif.'
_cod_original_formula_sum
'C78.50 H131.25 F6 Fe2.10 K N9 O8.62 Si3 Zn0.90'
_cod_database_code               1571015
_shelx_shelxl_version_number     2014/7
_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. Shared sites
{Zn02, Fe}
{Zn04, Fe1}
{Zn01, Fe2}
{Zn06, Fe3}
{Zn03, Fe4}
{Zn05, Fe5}
{C118, C318}
3. Rigid bond restraints
 C21S, C22S, O6S, C23S, C24S
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C17S, C18S, O5S, C19S, C20S
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C25S, C26S, O7S, C27S, C28S
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C118, F10, F11, F12
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C21S \\sim C22S \\sim O6S \\sim C23S \\sim C24S: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C17S \\sim C18S \\sim O5S \\sim C19S \\sim C20S: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
C25S \\sim C26S \\sim O7S \\sim C27S \\sim C28S \\sim C29S \\sim C30S \\sim O8S
\\sim C31S \\sim C32S: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C118 \\sim F10 \\sim F11 \\sim F12 \\sim C318 \\sim F10A \\sim F11A \\sim F12A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F12) = Uanis(F12A)
Uanis(F11) = Uanis(F11A)
Uanis(F10) = Uanis(F10A)
Uanis(Zn02) = Uanis(Fe)
Uanis(Zn04) = Uanis(Fe1)
Uanis(Zn01) = Uanis(Fe2)
Uanis(Zn06) = Uanis(Fe3)
Uanis(Zn03) = Uanis(Fe4)
Uanis(Zn05) = Uanis(Fe5)
Uanis(C9S) = Uanis(C9T)
Uanis(C10S) = Uanis(C10T)
Uanis(O3S) = Uanis(O3T)
Uanis(C11S) = Uanis(C11T)
Uanis(C12S) = Uanis(C12T)
Uanis(C13S) = Uanis(C17S)
Uanis(C14S) = Uanis(C18S)
Uanis(O4S) = Uanis(O5S)
Uanis(C15S) = Uanis(C19S)
Uanis(C16S) = Uanis(C20S)
Uanis(C29S) = Uanis(C28S)
Uanis(C27S) = Uanis(C30S)
Uanis(O7S) = Uanis(O8S)
Uanis(C26S) = Uanis(C31S)
Uanis(C25S) = Uanis(C32S)
Uanis(C118) = Uanis(C318)
5. Rigid body (RIGU) restrains
 C13S, C14S, O4S, C15S, C16S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Same fragment restrains
{C318, F10A, F11A, F12A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C118, F10, F11, F12}
{C9T, C10T, O3T, C11T, C12T} sigma for 1-2: 0.02, 1-3: 0.04
as
{C9S, C10S, O3S, C11S, C12S}
{C17S, C18S, O5S, C19S, C20S} sigma for 1-2: 0.02, 1-3: 0.04
{C21S, C22S, O6S, C23S, C24S} sigma for 1-2: 0.02, 1-3: 0.04
{C25S, C26S, O7S, C27S, C28S} sigma for 1-2: 0.02, 1-3: 0.04
{C29S, C30S, O8S, C31S, C32S} sigma for 1-2: 0.02, 1-3: 0.04
as
{C13S, C14S, O4S, C15S, C16S}
7. Others
 Sof(C318)=Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(1)
 Sof(C118)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(1)
 Sof(Fe)=Sof(Fe1)=Sof(Fe2)=Sof(Fe3)=Sof(Fe4)=Sof(Fe5)=1-FVAR(2)
 Sof(Zn01)=Sof(Zn02)=Sof(Zn03)=Sof(Zn04)=Sof(Zn05)=Sof(Zn06)=FVAR(2)
 Sof(C9T)=Sof(H9TA)=Sof(H9TB)=Sof(H9TC)=Sof(C10T)=Sof(H10O)=Sof(H10P)=Sof(O3T)=
 Sof(C11T)=Sof(H11H)=Sof(H11I)=Sof(C12T)=Sof(H12X)=Sof(H12Y)=Sof(H)=1-FVAR(3)
 Sof(C9S)=Sof(H9SA)=Sof(H9SB)=Sof(H9SC)=Sof(C10S)=Sof(H10M)=Sof(H10N)=Sof(O3S)=
 Sof(C11S)=Sof(H11F)=Sof(H11G)=Sof(C12S)=Sof(H12U)=Sof(H12V)=Sof(H12W)=FVAR(3)
 Sof(C17S)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18S)=Sof(H18D)=Sof(H18E)=
 Sof(O5S)=Sof(C19S)=Sof(H19A)=Sof(H19B)=Sof(C20S)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 0.75*(1-FVAR(5))
 Sof(C13S)=Sof(H13O)=Sof(H13P)=Sof(H13Q)=Sof(C14S)=Sof(H14A)=Sof(H14B)=
 Sof(O4S)=Sof(C15S)=Sof(H15A)=Sof(H15B)=Sof(C16S)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 0.75*FVAR(5)
 Sof(C29S)=Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30S)=Sof(H30D)=Sof(H30E)=
 Sof(O8S)=Sof(C31S)=Sof(H31A)=Sof(H31B)=Sof(C32S)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 1-FVAR(5)
 Sof(C25S)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26S)=Sof(H26D)=Sof(H26E)=
 Sof(O7S)=Sof(C27S)=Sof(H27A)=Sof(H27B)=Sof(C28S)=Sof(H28D)=Sof(H28E)=Sof(H28F)=
 FVAR(5)
 Fixed Sof: C21S(0.5) H21A(0.5) H21B(0.5) H21C(0.5) C22S(0.5) H22A(0.5)
 H22B(0.5) O6S(0.5) C23S(0.5) H23A(0.5) H23B(0.5) C24S(0.5) H24A(0.5) H24B(0.5)
 H24C(0.5)
8.a Ternary CH refined with riding coordinates:
 C2AA(H2AA), C8BA(H8BA), C71(H71), C73(H73), C69(H69), C3CA(H3CA)
8.b Secondary CH2 refined with riding coordinates:
 C4CA(H4CA,H4CB), C67(H67A,H67B), C66(H66A,H66B), C2(H2A,H2B), C70(H70A,H70B),
 C1BA(H1BA,H1BB), C74(H74A,H74B), C72(H72A,H72B), C65(H65A,H65B), C130(H13A,
 H13B), C64(H64A,H64B), C129(H12A,H12B), C132(H13C,H13D), C131(H13E,H13F),
 C63(H63A,H63B), C68(H68A,H68B), C60(H60A,H60B), C52(H52A,H52B), C62(H62A,H62B),
  C128(H12C,H12D), C133(H13G,H13H), C53(H53A,H53B), C135(H13I,H13J), C54(H54A,
 H54B), C127(H12E,H12F), C51(H51A,H51B), C136(H13K,H13L), C61(H61A,H61B),
 C56(H56A,H56B), C57(H57A,H57B), C59(H59A,H59B), C134(H13M,H13N), C58(H58A,
 H58B), C55(H55A,H55B), C120(H12G,H12H), C126(H12I,H12J), C119(H11D,H11E),
 C125(H12K,H12L), C121(H12M,H12N), C122(H12O,H12P), C124(H12Q,H12R), C123(H12S,
 H12T), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C6S(H6SA,H6SB), C7S(H7SA,H7SB),
 C10S(H10M,H10N), C11S(H11F,H11G), C10T(H10O,H10P), C11T(H11H,H11I), C14S(H14A,
 H14B), C15S(H15A,H15B), C18S(H18D,H18E), C19S(H19A,H19B), C22S(H22A,H22B),
 C23S(H23A,H23B), C26S(H26D,H26E), C27S(H27A,H27B), C30S(H30D,H30E), C31S(H31A,
 H31B)
8.c Me refined with riding coordinates:
 C13S(H13O,H13P,H13Q), C16S(H16A,H16B,H16C), C17S(H17A,H17B,H17C), C20S(H20A,
 H20B,H20C), C21S(H21A,H21B,H21C), C24S(H24A,H24B,H24C), C25S(H25D,H25E,H25F),
 C28S(H28D,H28E,H28F), C29S(H29D,H29E,H29F), C32S(H32A,H32B,H32C)
8.d Aromatic/amide H refined with riding coordinates:
 C48(H48), C44(H44), C116(H116), C112(H112), C32(H32), C33(H33), C23(H23),
 C35(H35), C5BA(H5BA), C34(H34), C2BA(H2BA), C9BA(H9BA), C79(H79), C76(H76),
 C22(H22), C77(H77), C46(H46), C8AA(H8AA), C103(H103), C21(H21), C3BA(H3BA),
 C91(H91), C90(H90), C88(H88), C114(H114), C78(H78), C102(H102), C89(H89),
 C100(H100), C101(H101)
8.e Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C25(H25A,H25B,H25C), C94(H94A,H94B,H94C), C0AA(H0AA,H0AB,
 H0AC), C30(H30A,H30B,H30C), C28(H28A,H28B,H28C), C98(H98A,H98B,H98C),
 C106(H10A,H10B,H10C), C93(H93A,H93B,H93C), C37(H37A,H37B,H37C), C96(H96A,H96B,
 H96C), C26(H26A,H26B,H26C), C97(H97A,H97B,H97C), C9AA(H9AA,H9AB,H9AC),
 C109(H10D,H10E,H10F), C29(H29A,H29B,H29C), C0BA(H0BA,H0BB,H0BC), C105(H10G,
 H10H,H10I), C110(H11A,H11B,H11C), C82(H82A,H82B,H82C), C85(H85A,H85B,H85C),
 C81(H81A,H81B,H81C), C108(H10J,H10K,H10L), C40(H40A,H40B,H40C), C18(H18A,H18B,
 H18C), C86(H86A,H86B,H86C), C4BA(H4BA,H4BB,H4BC), C41(H41A,H41B,H41C),
 C84(H84A,H84B,H84C), C42(H42A,H42B,H42C), C1S(H1SA,H1SB,H1SC), C4S(H4SA,H4SB,
 H4SC), C5S(H5SA,H5SB,H5SC), C8S(H8SA,H8SB,H8SC), C9S(H9SA,H9SB,H9SC),
 C12S(H12U,H12V,H12W), C9T(H9TA,H9TB,H9TC), C12T(H12X,H12Y,H)
;
_shelx_res_checksum              98307
_olex2_submission_special_instructions 'No special instructions were received'