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_7134706
_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_absolute_configuration ad
_chemical_formula_moiety
'C176 H112 Cr7 F8 Ni O32, C6 H16 N, 2(C3 H6 O), 2.5[C3H6O], 3.5[C3H6O]'
_chemical_formula_sum            'C206 H176 Cr7 F8 N Ni O40'
_chemical_formula_weight         3880.18
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_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            2
_cell_length_a                   31.9625(7)
_cell_length_b                   17.1553(5)
_cell_length_c                   16.9723(4)
_cell_measurement_reflns_used    23313
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      52.0680
_cell_measurement_theta_min      2.5960
_cell_volume                     9306.4(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection
'PROGRAM:BIS 2011.12.3.0/19-Dec-2011 && APEX2_2012.2-0                           '
_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      air
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.967
_diffrn_measured_fraction_theta_max 0.967
_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    -46.10  91.90   2.00  200.00    --  -66.31  73.87 102.16   69
  2  \w    -95.02  92.98   2.00  200.00    --  -65.23  73.87 171.13   94
  3  \w    -98.55  89.45   2.00  200.00    --  -68.76  73.87  39.57   94
  4  \w    -53.74 134.26   2.00  200.00    --  -23.95  73.87  72.76   94
  5  \w    -31.20  90.80   2.00  200.00    --  -66.91  73.87 137.19   61
  6  \w    -16.80  91.20   2.00  200.00    --  -67.01  73.87  76.50   54
  7  \w    -94.74  93.26   2.00  200.00    --  -64.95  73.87 -87.86   94
  8  \w      2.16 114.16   2.00  200.00    --  -23.55  73.87  -9.18   56
  9  \w    -63.26  94.74   2.00  200.00    --  -63.47  73.87 -37.05   79
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'Saxi-CrysAlisPro-abstract goniometer imported SAXI images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0478026000
_diffrn_orient_matrix_UB_12      -0.0100331000
_diffrn_orient_matrix_UB_13      0.0055227000
_diffrn_orient_matrix_UB_21      0.0057039000
_diffrn_orient_matrix_UB_22      0.0885080000
_diffrn_orient_matrix_UB_23      -0.0109273000
_diffrn_orient_matrix_UB_31      -0.0022202000
_diffrn_orient_matrix_UB_32      0.0114691000
_diffrn_orient_matrix_UB_33      0.0899434000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0744
_diffrn_reflns_av_unetI/netI     0.0560
_diffrn_reflns_Laue_measured_fraction_full 0.967
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            54143
_diffrn_reflns_point_group_measured_fraction_full 0.953
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        52.710
_diffrn_reflns_theta_max         52.710
_diffrn_reflns_theta_min         2.603
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.058
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.15658
_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    1.385
_exptl_crystal_description       block
_exptl_crystal_F_000             4014
_exptl_crystal_size_max          0.278
_exptl_crystal_size_mid          0.254
_exptl_crystal_size_min          0.129
_refine_diff_density_max         1.242
_refine_diff_density_min         -0.355
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.012(13)
_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     1272
_refine_ls_number_reflns         10232
_refine_ls_number_restraints     4220
_refine_ls_restrained_S_all      0.912
_refine_ls_R_factor_all          0.0924
_refine_ls_R_factor_gt           0.0679
_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^)+(0.1273P)^2^+11.8324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1793
_refine_ls_wR_factor_ref         0.2000
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    0.935
_reflns_Friedel_fraction_max     0.935
_reflns_number_gt                7793
_reflns_number_total             10232
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01911g2.cif
_cod_data_source_block           xrepw8
_cod_depositor_comments
'Adding full bibliography for 7134703--7134709.cif.'
_cod_database_code               7134706
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.623
_shelx_estimated_absorpt_t_min   0.398
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.98802
 0.01198
2. Shared sites
{Cr1, Ni1}
{Cr2, Ni2}
{Cr3, Ni3}
{Cr4, Ni4}
{Cr5, Ni5}
3. Restrained distances
 N1-C91 = N1-C92
 1.45 with sigma of 0.02
 C92-C94 = N1-C93 = C91-C92 = N1-C90 = C91-C89
 2.45 with sigma of 0.02
 C93-C94 = C93-C92 = C90-C89 = C90-C91
 1.54 with sigma of 0.02
 C13A-C12 \\sim C13-C12
 with sigma of 0.02
 C79A-C78 \\sim C79-C78
 with sigma of 0.02
4. Restrained planarity
 C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C12
 with sigma of 0.01
 C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A, C21A, C22A, C12
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim
C21 \\sim C22 \\sim C13A \\sim C14A \\sim C15A \\sim C16A \\sim C17A \\sim C18A
\\sim C19A \\sim C20A \\sim C21A \\sim C22A: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C79 \\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C86 \\sim C87 \\sim
C88 \\sim C79A \\sim C80A \\sim C81A \\sim C82A \\sim C83A \\sim C84A \\sim
C85A \\sim C86A \\sim C85 \\sim C87A \\sim C88A: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 2A
N1 \\sim C92 \\sim C91 \\sim C93 \\sim C90 \\sim C94 \\sim C89: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
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)
6. Rigid body (RIGU) restrains
 C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C13A, C14A, C15A, C16A,
 C17A, C18A, C19A, C20A, C21A, C22A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C79, C80, C81, C82, C83, C84, C86, C87, C88, C79A, C80A, C81A, C82A, C83A,
 C84A, C85A, C86A, C85, C87A, C88A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N1, C92, C91, C93, C90, C94, C89
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Same fragment restrains
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02,
1-3: 0.04
as in
{O9, O10, C45, C46, C47, C48, C49, C50, C51, C52, C53, C54, C55}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02,
1-3: 0.04
as in
{O11, O12, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02,
1-3: 0.04
as in
{O15, O16, C78, C79, C80, C81, C82, C83, C84, C85, C86, C87, C88}
{C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A, C21A, C22A}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02,
1-3: 0.04
as in
{O5, O6, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33}
{C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C79A, C80A, C81A, C82A, C83A, C84A, C85A, C86A, C87A, C88A}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02,
1-3: 0.04
as in
{O13, O14, C67, C68, C69, C70, C71, C72, C73, C74, C75, C76, C77}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02,
1-3: 0.04
as in
{O3, O4, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22}
{O1, O2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11} sigma for 1-2: 0.02,
1-3: 0.04
as in
{O7, O8, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44}
8. Others
 Sof(C79A)=Sof(C80A)=Sof(H80A)=Sof(C81A)=Sof(H81A)=Sof(C82A)=Sof(H82A)=
 Sof(C83A)=Sof(C84A)=Sof(C85A)=Sof(H85A)=Sof(C86A)=Sof(H86A)=Sof(C87A)=
 Sof(H87A)=Sof(C88A)=Sof(H88A)=1-FVAR(1)
 Sof(C79)=Sof(C80)=Sof(H80)=Sof(C81)=Sof(H81)=Sof(C82)=Sof(H82)=Sof(C83)=
 Sof(C84)=Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=
 Sof(H88)=FVAR(1)
 Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=
 Sof(H21A)=Sof(C22A)=Sof(H22A)=1-FVAR(2)
 Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16)=Sof(C17)=
 Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=
 Sof(H22)=FVAR(2)
 Fixed Sof: Cr1(0.4375) Cr2(0.875) Cr3(0.875) Cr4(0.875) Cr5(0.4375)
 Ni1(0.0625) Ni2(0.125) Ni3(0.125) Ni4(0.125) Ni5(0.0625) N1(0.5) H1A(0.5)
 H1B(0.5) C94(0.5) H94A(0.5) H94B(0.5) H94C(0.5) C92(0.5) H92A(0.5) H92B(0.5)
 C93(0.5) H93A(0.5) H93B(0.5) C90(0.5) H90A(0.5) H90B(0.5) C91(0.5) H91A(0.5)
 H91B(0.5) C89(0.5) H89A(0.5) H89B(0.5) H89C(0.5)
9.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), C92(H92A,H92B), C93(H93A,H93B), C90(H90A,H90B), C91(H91A,H91B)
9.b Me refined with riding coordinates:
 C94(H94A,H94B,H94C), C036(H03A,H03B,H03C), C02E(H02A,H02B,H02C), C89(H89A,
 H89B,H89C)
9.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C16(H16), C19(H19), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26),
  C27(H27), C30(H30), C31(H31), C32(H32), C33(H33), C36(H36), C37(H37),
 C38(H38), C41(H41), C42(H42), C43(H43), C44(H44), C47(H47), C48(H48), C49(H49),
  C52(H52), C53(H53), C54(H54), C55(H55), C58(H58), C59(H59), C60(H60),
 C63(H63), C64(H64), C65(H65), C66(H66), C69(H69), C70(H70), C71(H71), C74(H74),
  C75(H75), C76(H76), C77(H77), C80(H80), C81(H81), C82(H82), C85(H85),
 C86(H86), C87(H87), C88(H88), C80A(H80A), C81A(H81A), C82A(H82A), C85A(H85A),
 C86A(H86A), C87A(H87A), C88A(H88A), C14A(H14A), C15A(H15A), C16A(H16A),
 C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              32296
_shelx_hkl_checksum              40626
_shelx_fab_checksum              74649
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.464
_oxdiff_exptl_absorpt_empirical_full_min 0.600