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_7134704
_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         'C128 H112 Cr7 F8 Ni O32, C6 H16 N'
_chemical_formula_sum            'C134 H128 Cr7 F8 N Ni O32'
_chemical_formula_weight         2839.08
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_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                 94.616(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.0332(4)
_cell_length_b                   24.0911(5)
_cell_length_c                   23.7630(6)
_cell_measurement_reflns_used    29896
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      25.4970
_cell_measurement_theta_min      1.6370
_cell_volume                     13713.8(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection       'GDA - generic data acquisition software'
_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_temperature      100.00(10)
_diffrn_detector                 'Photon counting pixel array'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Dectris PILATUS 2M'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f      0.00 179.00   1.00    0.20   0.00   0.00   0.00    --   179
  2  \w   -145.00  24.00   1.00    0.20    --   30.00   0.00   0.00  169
  3  \w   -145.00  24.00   1.00    0.20    --   30.00   0.00 120.00  169
  4  \w   -145.00  24.00   1.00    0.20    --   30.00   0.00 240.00  169
;
_diffrn_measurement_device       'Fixed \c 3-circle diffractometer'
_diffrn_measurement_device_type  'Fluid Film Devices'
_diffrn_measurement_method       'shutterless scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroMount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0243076000
_diffrn_orient_matrix_UB_12      0.0150994000
_diffrn_orient_matrix_UB_13      -0.0043046000
_diffrn_orient_matrix_UB_21      0.0031525000
_diffrn_orient_matrix_UB_22      0.0090885000
_diffrn_orient_matrix_UB_23      0.0275591000
_diffrn_orient_matrix_UB_31      0.0150413000
_diffrn_orient_matrix_UB_32      0.0225147000
_diffrn_orient_matrix_UB_33      -0.0082554000
_diffrn_radiation_monochromator  'Silicon 111'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.0593
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            90883
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        24.415
_diffrn_reflns_theta_max         25.491
_diffrn_reflns_theta_min         1.468
_diffrn_source                   Synchrotron
_diffrn_source_details           'Allan et al. (2017)'
_diffrn_source_type              'Diamond Light Source Beamline I19-1'
_exptl_absorpt_coefficient_mu    0.694
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59716
_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    1.375
_exptl_crystal_description       block
_exptl_crystal_F_000             5852
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.187
_exptl_crystal_size_min          0.054
_refine_diff_density_max         1.064
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1644
_refine_ls_number_reflns         14008
_refine_ls_number_restraints     6300
_refine_ls_restrained_S_all      0.950
_refine_ls_R_factor_all          0.0844
_refine_ls_R_factor_gt           0.0694
_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^)+(0.1475P)^2^+18.7386P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2195
_refine_ls_wR_factor_ref         0.2340
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10485
_reflns_number_total             14008
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01911g2.cif
_cod_data_source_block           m_gt80-12_2_c1_
_cod_depositor_comments
'Adding full bibliography for 7134703--7134709.cif.'
_cod_database_code               7134704
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.879
_olex2_refinement_description
;
1. Shared sites
{Cr1, Ni1}
{Cr2, Ni2}
{Cr3, Ni3}
{Cr4, Ni4}
{Cr5, Ni5}
{Cr6, Ni6}
{Cr7, Ni7}
{Cr8, Ni8}
2. Restrained distances
 N022-C129
 2.45 with sigma of 0.02
 N022-C01C = N022-C01B
 1.45 with sigma of 0.02
 C130-N022
 2.45 with sigma of 0.02
 C130-C01C = C130-C01W = C129-C01B = C129-C01V
 1.54 with sigma of 0.02
 C01V-C01B = C01C-C01W
 2.45 with sigma of 0.02
 C01C-C01B
 2.45 with sigma of 0.02
3. Restrained planarity
 C1, C2, C3, C4, C5, C6, C7, C8
 with sigma of 0.01
 C9, C10, C11, C12, C13, C14, C15, C16
 with sigma of 0.01
 C17, C18, C19, C20, C21, C22, C23, C24
 with sigma of 0.01
 C25, C26, C27, C28, C29, C30, C31, C32
 with sigma of 0.01
 C33, C34, C35, C36, C37, C38, C39, C40
 with sigma of 0.01
 C41, C42, C43, C44, C45, C46, C47, C48
 with sigma of 0.01
 C49, C50, C51, C52, C53, C54, C55, C56
 with sigma of 0.01
 C57, C58, C59, C60, C61, C62, C63, C64
 with sigma of 0.01
 C65, C66, C67, C68, C69, C70, C71, C72
 with sigma of 0.01
 C80, C73, C74, C75, C76, C77, C78, C79
 with sigma of 0.01
 C81, C82, C83, C84, C85, C86, C87, C88
 with sigma of 0.01
 C89, C90, C91, C92, C93, C94, C95, C96
 with sigma of 0.01
 C97, C98, C99, C100, C101, C102, C103, C104
 with sigma of 0.01
 C105, C106, C107, C108, C109, C110, C111, C112
 with sigma of 0.01
 C113, C114, C115, C116, C117, C118, C119, C120
 with sigma of 0.01
 C121, C122, C123, C124, C125, C126, C127, C128
 with sigma of 0.01
4. 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(Cr1) = Uanis(Ni1)
Uanis(Cr2) = Uanis(Ni2)
Uanis(Cr3) = Uanis(Ni3)
Uanis(Cr4) = Uanis(Ni4)
Uanis(Cr5) = Uanis(Ni5)
Uanis(Cr6) = Uanis(Ni6)
Uanis(Cr7) = Uanis(Ni7)
Uanis(Cr8) = Uanis(Ni8)
5. 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
6. Same fragment restrains
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O3, O4, C9, C10, C11, C12, C13, C14, C15, C16}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O7, O8, C25, C26, C27, C28, C29, C30, C31, C32}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O19, O20, C73, C74, C75, C76, C77, C78, C79, C80}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O5, O6, C17, C18, C19, C20, C21, C22, C23, C24}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O13, O14, C49, C50, C51, C52, C53, C54, C55, C56}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O31, O32, C121, C122, C123, C124, C125, C126, C127, C128}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O23, O24, C89, C90, C91, C92, C93, C94, C95, C96}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O11, O12, C41, C42, C43, C44, C45, C46, C47, C48}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O27, O28, C105, C106, C107, C108, C109, C110, C111, C112}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O29, O30, C113, C114, C115, C116, C117, C118, C119, C120}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O25, O26, C97, C98, C99, C100, C101, C102, C103, C104}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O17, O18, C65, C66, C67, C68, C69, C70, C71, C72}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O21, O22, C81, C82, C83, C84, C85, C86, C87, C88}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O15, O16, C57, C58, C59, C60, C61, C62, C63, C64}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O9, O10, C33, C34, C35, C36, C37, C38, C39, C40}
7. Others
 Fixed Sof: Cr1(0.4375) Cr2(0.4375) Cr3(0.4375) Cr4(0.4375) Cr5(0.4375)
 Cr6(0.4375) Cr7(0.4375) Cr8(0.4375) Ni1(0.0625) Ni2(0.0625) Ni3(0.0625)
 Ni4(0.0625) Ni5(0.0625) Ni6(0.0625) Ni7(0.0625) Ni8(0.0625) F1(0.5) F2(0.5)
 F3(0.5) F4(0.5) F5(0.5) F6(0.5) F7(0.5) F8(0.5) O1(0.5) O2(0.5) C1(0.5)
 C2(0.5) C3(0.5) H3(0.5) C4(0.5) H4(0.5) C5(0.5) H5(0.5) C6(0.5) C7(0.5)
 H7(0.5) C8(0.5) H8A(0.5) H8B(0.5) H8C(0.5) O3(0.5) O4(0.5) C9(0.5) C10(0.5)
 C11(0.5) H11(0.5) C12(0.5) H12(0.5) C13(0.5) H13(0.5) C14(0.5) C15(0.5)
 H15(0.5) C16(0.5) H16A(0.5) H16B(0.5) H16C(0.5) O5(0.5) O6(0.5) C17(0.5)
 C18(0.5) C19(0.5) H19(0.5) C20(0.5) H20(0.5) C21(0.5) H21(0.5) C22(0.5)
 C23(0.5) H23(0.5) C24(0.5) H24A(0.5) H24B(0.5) H24C(0.5) O7(0.5) O8(0.5)
 C25(0.5) C26(0.5) C27(0.5) H27(0.5) C28(0.5) H28(0.5) C29(0.5) H29(0.5)
 C30(0.5) C31(0.5) H31(0.5) C32(0.5) H32A(0.5) H32B(0.5) H32C(0.5) O9(0.5)
 O10(0.5) C33(0.5) C34(0.5) C35(0.5) H35(0.5) C36(0.5) H36(0.5) C37(0.5)
 H37(0.5) C38(0.5) C39(0.5) H39(0.5) C40(0.5) H40A(0.5) H40B(0.5) H40C(0.5)
 O11(0.5) O12(0.5) C41(0.5) C42(0.5) C43(0.5) H43(0.5) C44(0.5) H44(0.5)
 C45(0.5) H45(0.5) C46(0.5) C47(0.5) H47(0.5) C48(0.5) H48A(0.5) H48B(0.5)
 H48C(0.5) O13(0.5) O14(0.5) C49(0.5) C50(0.5) C51(0.5) H51(0.5) C52(0.5)
 H52(0.5) C53(0.5) H53(0.5) C54(0.5) C55(0.5) H55(0.5) C56(0.5) H56A(0.5)
 H56B(0.5) H56C(0.5) O15(0.5) O16(0.5) C57(0.5) C58(0.5) C59(0.5) H59(0.5)
 C60(0.5) H60(0.5) C61(0.5) H61(0.5) C62(0.5) C63(0.5) H63(0.5) C64(0.5)
 H64A(0.5) H64B(0.5) H64C(0.5) O17(0.5) O18(0.5) C65(0.5) C66(0.5) C67(0.5)
 H67(0.5) C68(0.5) H68(0.5) C69(0.5) H69(0.5) C70(0.5) C71(0.5) H71(0.5)
 C72(0.5) H72A(0.5) H72B(0.5) H72C(0.5) O19(0.5) O20(0.5) C73(0.5) C74(0.5)
 C75(0.5) H75(0.5) C76(0.5) H76(0.5) C77(0.5) H77(0.5) C78(0.5) C79(0.5)
 H79(0.5) C80(0.5) H80A(0.5) H80B(0.5) H80C(0.5) O21(0.5) O22(0.5) C81(0.5)
 C82(0.5) C83(0.5) H83(0.5) C84(0.5) H84(0.5) C85(0.5) H85(0.5) C86(0.5)
 C87(0.5) H87(0.5) C88(0.5) H88A(0.5) H88B(0.5) H88C(0.5) O23(0.5) O24(0.5)
 C89(0.5) C90(0.5) C91(0.5) H91(0.5) C92(0.5) H92(0.5) C93(0.5) H93(0.5)
 C94(0.5) C95(0.5) H95(0.5) C96(0.5) H96A(0.5) H96B(0.5) H96C(0.5) O25(0.5)
 O26(0.5) C97(0.5) C98(0.5) C99(0.5) H99(0.5) C100(0.5) H100(0.5) C101(0.5)
 H101(0.5) C102(0.5) C103(0.5) H103(0.5) C104(0.5) H10A(0.5) H10B(0.5)
 H10C(0.5) O27(0.5) O28(0.5) C105(0.5) C106(0.5) C107(0.5) H107(0.5) C108(0.5)
 H108(0.5) C109(0.5) H109(0.5) C110(0.5) C111(0.5) H111(0.5) C112(0.5)
 H11A(0.5) H11B(0.5) H11C(0.5) O29(0.5) O30(0.5) C113(0.5) C114(0.5) C115(0.5)
 H115(0.5) C116(0.5) H116(0.5) C117(0.5) H117(0.5) C118(0.5) C119(0.5)
 H119(0.5) C120(0.5) H12A(0.5) H12B(0.5) H12C(0.5) O31(0.5) O32(0.5) C121(0.5)
 C122(0.5) C123(0.5) H123(0.5) C124(0.5) H124(0.5) C125(0.5) H125(0.5)
 C126(0.5) C127(0.5) H127(0.5) C128(0.5) H12D(0.5) H12E(0.5) H12F(0.5)
 N022(0.5) H02A(0.5) H02B(0.5) C129(0.5) H12G(0.5) H12H(0.5) C130(0.5)
 H13A(0.5) H13B(0.5) C01B(0.5) H01A(0.5) H01B(0.5) C01C(0.5) H01C(0.5)
 H01D(0.5) C01V(0.5) H01E(0.5) H01F(0.5) H01G(0.5) C01W(0.5) H01H(0.5)
 H01I(0.5) H01J(0.5)
8.a Secondary CH2 refined with riding coordinates:
 N022(H02A,H02B), C129(H12G,H12H), C130(H13A,H13B), C01B(H01A,H01B), C01C(H01C,
 H01D)
8.b Me refined with riding coordinates:
 C8(H8A,H8B,H8C), C16(H16A,H16B,H16C), C24(H24A,H24B,H24C), C32(H32A,H32B,
 H32C), C40(H40A,H40B,H40C), C48(H48A,H48B,H48C), C56(H56A,H56B,H56C), C64(H64A,
 H64B,H64C), C72(H72A,H72B,H72C), C80(H80A,H80B,H80C), C88(H88A,H88B,H88C),
 C96(H96A,H96B,H96C), C104(H10A,H10B,H10C), C112(H11A,H11B,H11C), C120(H12A,
 H12B,H12C), C128(H12D,H12E,H12F), C01V(H01E,H01F,H01G), C01W(H01H,H01I,H01J)
8.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C7(H7), C11(H11), C12(H12), C13(H13), C15(H15),
 C19(H19), C20(H20), C21(H21), C23(H23), C27(H27), C28(H28), C29(H29), C31(H31),
  C35(H35), C36(H36), C37(H37), C39(H39), C43(H43), C44(H44), C45(H45),
 C47(H47), C51(H51), C52(H52), C53(H53), C55(H55), C59(H59), C60(H60), C61(H61),
  C63(H63), C67(H67), C68(H68), C69(H69), C71(H71), C75(H75), C76(H76),
 C77(H77), C79(H79), C83(H83), C84(H84), C85(H85), C87(H87), C91(H91), C92(H92),
  C93(H93), C95(H95), C99(H99), C100(H100), C101(H101), C103(H103), C107(H107),
 C108(H108), C109(H109), C111(H111), C115(H115), C116(H116), C117(H117),
 C119(H119), C123(H123), C124(H124), C125(H125), C127(H127)
;
_shelx_res_checksum              17681
_shelx_hkl_checksum              87347
_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 1.364
_oxdiff_exptl_absorpt_empirical_full_min 0.684