Energetics of carboxylate-metal bonds in polymetallic rings.
Geue, Niklas; Renningholtz, Tim; Whitehead, George F. S.; Timco, Grigore A.; Trujillo, Cristina; Barran, Perdita E.; Winpenny, Richard E. P.; Chemical communications (Cambridge, England) 61 (2025) 11049–11052; doi:10.1039/d5cc01911g

data_7134705
_publ_section_title
;
 Energetics of carboxylate-metal bonds in polymetallic rings.
;
_journal_issue                   59
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              11049
_journal_page_last               11052
_journal_paper_doi               10.1039/d5cc01911g
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety
'C80 H48 Cr7 F8 Ni O48, C6 H16 N1, 2(C2 H3 N), 6[C2H3N]'
_chemical_formula_sum            'C102 H88 Cr7 F8 N9 Ni O48'
_chemical_formula_weight         2782.52
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-17
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-03-17 deposited with the CCDC.	2025-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.8743(8)
_cell_length_b                   27.9440(6)
_cell_length_c                   16.9778(5)
_cell_measurement_reflns_used    12195
_cell_measurement_temperature    99.95(10)
_cell_measurement_theta_max      28.0810
_cell_measurement_theta_min      3.2390
_cell_volume                     12749.9(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlis system (CCD Version 1.171.32.24 (release 21-04-2008 CrysAlis171 .NET))'
_computing_data_reduction        'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.3367
_diffrn_detector_type            'Sapphire2, large Be window'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.895
_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    -64.00  40.00   1.00  223.80    --  -21.07 -20.00 113.00  104
  2  \w     28.00  73.00   1.00  223.80    --   22.48-106.00 269.00   45
  3  \w    -19.00  14.00   1.00  223.80    --   22.48-106.00 352.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire2, large Be window'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0192309000
_diffrn_orient_matrix_UB_12      0.0064277000
_diffrn_orient_matrix_UB_13      -0.0266524000
_diffrn_orient_matrix_UB_21      0.0169123000
_diffrn_orient_matrix_UB_22      -0.0019444000
_diffrn_orient_matrix_UB_23      -0.0318579000
_diffrn_orient_matrix_UB_31      -0.0064191000
_diffrn_orient_matrix_UB_32      -0.0244701000
_diffrn_orient_matrix_UB_33      -0.0044828000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0502
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.895
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            38968
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.511
_diffrn_reflns_theta_min         2.838
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.816
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63423
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.142a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.450
_exptl_crystal_description       block
_exptl_crystal_F_000             5660
_exptl_crystal_size_max          0.55
_exptl_crystal_size_mid          0.289
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.654
_refine_diff_density_min         -0.600
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1031
_refine_ls_number_reflns         14760
_refine_ls_number_restraints     4228
_refine_ls_restrained_S_all      0.941
_refine_ls_R_factor_all          0.0781
_refine_ls_R_factor_gt           0.0529
_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^)+(0.0955P)^2^+0.0351P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1430
_refine_ls_wR_factor_ref         0.1595
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10271
_reflns_number_total             14760
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01911g2.cif
_cod_data_source_block           orepw1107
_cod_depositor_comments
'Adding full bibliography for 7134703--7134709.cif.'
_cod_database_code               7134705
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         Cr7Ni1F8O32C90H150N1
_shelx_estimated_absorpt_t_max   0.874
_shelx_estimated_absorpt_t_min   0.662
_olex2_refinement_description
;
1. Shared sites
{C6, C6A}
{C16A, C16}
{C21A, C21}
{C22A, C22}
{C26, C26A}
{C51, C51A}
{C56A, C56}
{C27, C27A}
{C17, C17A}
{Cr1, Ni1}
{Cr2, Ni2}
{Cr3, Ni3}
{Cr4, Ni4}
2. Restrained distances
 N1-C53 = N1-C54
 1.45 with sigma of 0.02
 C51-C53 = N1-C52 = C53-C54 = N1-C55 = C56-C54
 2.45 with sigma of 0.02
 C56-C55 = C55-C54 = C52-C53 = C52-C51
 1.54 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(Cr3) = Uanis(Ni3)
Uanis(Cr4) = Uanis(Ni4)
Uanis(Cr2) = Uanis(Ni2)
Uanis(Cr1) = Uanis(Ni1)
Uanis(C6) = Uanis(C6A)
Uanis(C16A) = Uanis(C16)
Uanis(C17) = Uanis(C17A)
Uanis(C21A) = Uanis(C21)
Uanis(C22A) = Uanis(C22)
Uanis(C26) = Uanis(C26A)
Uanis(C27) = Uanis(C27A)
Uanis(C51) = Uanis(C51A)
Uanis(C56A) = Uanis(C56)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O21, O22, C36, C37, C38, C39, C40}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O25, O26, C46, C47, C48, C49, C50}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O16, O18, C26, C27, C28, C29, C30}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O23, O24, C41, C42, C43, C44, C45}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O7, O9, C11, C12, C13, C14, C15}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O1, O3, C1, C2, C3, C4, C5}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O11, O12, C16, C17, C18, C19, C20}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O4, O6, C6, C7, C8, C9, C10}
{N1, C51, C52, C53, C54, C55, C56} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1A, C51A, C52A, C53A, C54A, C55A, C56A}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O17, O18A, C26A, C27A, C28A, C29A, C30A}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O14, O15A, C21A, C22A, C23A, C24A, C25A}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O13, O15, C21, C22, C23, C24, C25}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O10, O12A, C16A, C17A, C18A, C19A, C20A}
{O19, O20, C31, C32, C33, C34, C35} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O5, O6A, C6A, C7A, C8A, C9A, C10A}
6. Others
 Sof(O6A)=Sof(C6A)=Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=
 Sof(H10A)=1-FVAR(1)
 Sof(O6)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=
 FVAR(1)
 Sof(O12A)=Sof(C16A)=Sof(C17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=
 Sof(C20A)=Sof(H20A)=1-FVAR(2)
 Sof(O12)=Sof(C16)=Sof(C17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(H19)=Sof(C20)=
 Sof(H20)=FVAR(2)
 Sof(O15A)=Sof(C21A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=
 Sof(C25A)=Sof(H25A)=Sof(O18A)=Sof(C26A)=Sof(C27A)=Sof(C28A)=Sof(H28A)=
 Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=1-FVAR(3)
 Sof(O15)=Sof(C21)=Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=
 Sof(H25)=Sof(O18)=Sof(C26)=Sof(C27)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=
 Sof(C30)=Sof(H30)=FVAR(3)
 Sof(N1A)=Sof(H1AA)=Sof(H1AB)=Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=
 Sof(C52A)=Sof(H52C)=Sof(H52D)=Sof(C53A)=Sof(H53C)=Sof(H53D)=Sof(C54A)=
 Sof(H54C)=Sof(H54D)=Sof(C55A)=Sof(H55C)=Sof(H55D)=Sof(C56A)=Sof(H56D)=
 Sof(H56E)=Sof(H56F)=0.5*(1-FVAR(5))
 Sof(N1)=Sof(H1A)=Sof(H1B)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=
 Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=0.5*FVAR(5)
 Fixed Sof: Cr3(0.875) Cr4(0.875) Cr2(0.875) Cr1(0.875) Ni3(0.125) Ni4(0.125)
 Ni2(0.125) Ni1(0.125) O20(0.5) C33(0.5) H33(0.5) C34(0.5) H34(0.5) C35(0.5)
 H35(0.5) O22(0.5) C38(0.5) H38(0.5) C39(0.5) H39(0.5) C40(0.5) H40(0.5)
 O24(0.5) C43(0.5) H43(0.5) C44(0.5) H44(0.5) C45(0.5) H45(0.5) O26(0.5)
 C47(0.5) C48(0.5) H48(0.5) C49(0.5) H49(0.5) C50(0.5) H50(0.5)
7.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B),
 N1A(H1AA,H1AB), C52A(H52C,H52D), C53A(H53C,H53D), C54A(H54C,H54D), C55A(H55C,
 H55D)
7.b Me refined with riding coordinates:
 C51(H51A,H51B,H51C), C56(H56A,H56B,H56C), C51A(H51D,H51E,H51F), C56A(H56D,
 H56E,H56F)
7.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C34(H34), C35(H35), C38(H38), C39(H39), C40(H40), C43(H43),
 C44(H44), C45(H45), C48(H48), C49(H49), C50(H50), C3(H3), C4(H4), C5(H5),
 C8(H8), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15), C18A(H18A), C19A(H19A),
  C20A(H20A), C23(H23), C24(H24), C25(H25), C28(H28), C29(H29), C30(H30),
 C8A(H8A), C9A(H9A), C10A(H10A), C18(H18), C19(H19), C20(H20), C23A(H23A),
 C24A(H24A), C25A(H25A), C28A(H28A), C29A(H29A), C30A(H30A)
7.d Idealised Me refined with riding coordinates:
 C60(H60A,H60B,H60C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              41342
_shelx_hkl_checksum              23970
_shelx_fab_checksum              68864
_olex2_date_sample_data_collection 2016-02-03
_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 1.309
_oxdiff_exptl_absorpt_empirical_full_min 0.839