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_7134707
_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
'C208 H272 Cr7 F8 Ni O80, C6 H16 N, 16[C2H3N], 2.5[C2H3N]'
_chemical_formula_sum            'C251 H343.5 Cr7 F8 N19.5 Ni O80'
_chemical_formula_weight         5488.64
_space_group_crystal_system      tetragonal
_space_group_IT_number           130
_space_group_name_Hall           '-P 4a 2ac'
_space_group_name_H-M_alt        'P 4/n c c :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            4
_cell_length_a                   26.7607(9)
_cell_length_b                   26.7607(9)
_cell_length_c                   40.561(3)
_cell_measurement_reflns_used    20977
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      53.0110
_cell_measurement_theta_min      2.2500
_cell_volume                     29047(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection
'PROGRAM:BIS 2011.12.3.0/19-Dec-2011 && APEX2_2013.4-1                           '
_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 0.949
_diffrn_measured_fraction_theta_max 0.949
_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     30.31 218.72   1.20   10.00    --   60.00  73.87 169.21  157
  2  \w    117.11 228.72   1.20   10.00    --   70.00  73.87  14.21   93
  3  \w     75.74 205.34   1.20   10.00    --   60.00  73.87  94.21  108
  4  \w     -4.49 119.11   1.20   10.00    --   25.00  73.87-130.79  103
  5  \w     -1.77  73.83   1.20   10.00    --    3.00  73.87 124.21   63
;
_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      0.0494691000
_diffrn_orient_matrix_UB_12      -0.0224492000
_diffrn_orient_matrix_UB_13      -0.0124480000
_diffrn_orient_matrix_UB_21      -0.0202037000
_diffrn_orient_matrix_UB_22      0.0005705000
_diffrn_orient_matrix_UB_23      -0.0355197000
_diffrn_orient_matrix_UB_31      0.0211467000
_diffrn_orient_matrix_UB_32      0.0530219000
_diffrn_orient_matrix_UB_33      -0.0049042000
_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  0.0647
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 0.949
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            75476
_diffrn_reflns_point_group_measured_fraction_full 0.949
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        53.904
_diffrn_reflns_theta_max         53.904
_diffrn_reflns_theta_min         2.178
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.869
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45079
_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    1.255
_exptl_crystal_description       block
_exptl_crystal_F_000             11576
_exptl_crystal_size_max          0.325
_exptl_crystal_size_mid          0.278
_exptl_crystal_size_min          0.215
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.294
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     897
_refine_ls_number_reflns         8330
_refine_ls_number_restraints     2210
_refine_ls_restrained_S_all      0.986
_refine_ls_R_factor_all          0.1347
_refine_ls_R_factor_gt           0.0884
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1898P)^2^+14.8511P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2616
_refine_ls_wR_factor_ref         0.2997
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4900
_reflns_number_total             8330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01911g2.cif
_cod_data_source_block           xrepw301
_cod_depositor_comments
'Adding full bibliography for 7134703--7134709.cif.'
_cod_original_sg_symbol_H-M      'P 4/n c c'
_cod_original_formula_sum        'C251 H343.50 Cr7 F8 N19.50 Ni O80'
_cod_database_code               7134707
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.577
_shelx_estimated_absorpt_t_min   0.456
_olex2_refinement_description
;
1. Shared sites
{C1, C1A}
{Cr1, Ni1}
{Cr2, Ni2}
2. Restrained distances
 C50-C49 = C24A-C23A = C24-C23 = C37-C36 = C11A-C10A = C11-C10
 1.54 with sigma of 0.02
 C54-C53 = C55-C54 = C57-C56 = C58-C57
 1.54 with sigma of 0.02
 C55-C53 = N1-C54 = C56-C55 = N1-C57 = C58-C56
 2.45 with sigma of 0.02
 N1-C56 = N1-C55
 1.45 with sigma of 0.02
 C2-C1 \\sim C2A-C1
 with sigma of 0.02
 O9-C23 \\sim O9-C23A
 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(Cr1) = Uanis(Ni1)
Uanis(Cr2) = Uanis(Ni2)
Uanis(C1) = Uanis(C1A)
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
{C23, C24} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C23A, C24A}
{O1, O2, O3, O4, O5, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{O11, O12, O13, O14, O15, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36,
C37, C38, C39}
{O1, O2, O3, O4, O5, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{O16, O17, O18, O19, O20, C40, C41, C42, C43, C44, C45, C46, C47, C48, C49,
C50, C51, C52}
{O3, O4, O5, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13} sigma for
1-2: 0.02, 1-3: 0.04
as in
{O3A, O4A, O5A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A,
C13A}
{O1, O2, O3, O4, O5, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13}
sigma for 1-2: 0.02, 1-3: 0.04
as in
{O6, O7, O8, O9, O10, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24,
C25, C26}
6. Others
 Sof(C23A)=Sof(H23C)=Sof(H23D)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(1)
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(1)
 Sof(O3A)=Sof(O4A)=Sof(O5A)=Sof(C1A)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(C5A)=Sof(C6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=
 Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10C)=Sof(H10D)=Sof(C11A)=
 Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C12A)=Sof(H12C)=Sof(H12D)=Sof(C13A)=
 Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(2)
 Sof(O3)=Sof(O4)=Sof(O5)=Sof(C1)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(C5)=
 Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=
 Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(2)
 Fixed Sof: Cr1(0.875) Cr2(0.875) Ni1(0.125) Ni2(0.125) H58A(0.25) H58C(0.25)
 H58B(0.25) C54(0.25) H54A(0.25) H54B(0.25) C53(0.25) H53A(0.25) H53B(0.25)
 H53C(0.25) C56(0.25) H56A(0.25) H56B(0.25) N1(0.25) H1A(0.25) H1B(0.25)
 C57(0.25) H57A(0.25) H57B(0.25) C55(0.25) H55A(0.25) H55B(0.25)
7.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C10(H10A,H10B), C12(H12A,H12B), C21(H21A,H21B), C23(H23A,H23B),
 C25(H25A,H25B), C23A(H23C,H23D), C34(H34A,H34B), C36(H36A,H36B), C38(H38A,
 H38B), C47(H47A,H47B), C49(H49A,H49B), C51(H51A,H51B), C54(H54A,H54B),
 C56(H56A,H56B), N1(H1A,H1B), C57(H57A,H57B), C55(H55A,H55B), C8A(H8AA,H8AB),
 C10A(H10C,H10D), C12A(H12C,H12D)
7.b Me refined with riding coordinates:
 C9(H9A,H9B,H9C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C24A(H24D,H24E,H24F),
 C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C48(H48A,H48B,
 H48C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C), C58(H58A,H58C,H58B), C53(H53A,
 H53B,H53C), C9A(H9AA,H9AB,H9AC), C11A(H11D,H11E,H11F), C13A(H13D,H13E,H13F)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C16(H16), C20(H20), C29(H29), C33(H33), C42(H42), C46(H46),
 C3A(H3A), C7A(H7A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24326
_shelx_hkl_checksum              40619
_shelx_fab_checksum              98192
_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 1.596
_oxdiff_exptl_absorpt_empirical_full_min 0.640