A graceful break-up: serendipitous self-assembly of a ferromagnetically coupled [NiII14] wheel
Brechin, Euan K.; Agapaki, Eleftheria; Singh, Mukesh; Tsanai, Angelos B.; Nichol, Gary Stephen; Schnack, Jürgen; Chemical Communications  (2022) –; doi:10.1039/D2CC03445J

data_7130321
_publ_section_title
;
 A graceful break-up: serendipitous self-assembly of a ferromagnetically
 coupled [NiII14] wheel
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC03445J
_journal_year                    2022
_chemical_formula_moiety         'C75 H116 Cl14 N24 Ni14 O30, 4(C3 H6 O)'
_chemical_formula_sum            'C87 H140 Cl14 N24 Ni14 O34'
_chemical_formula_weight         3384.46
_chemical_name_systematic        EA-416_Acetone
_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_Hall           '-P 4bc'
_space_group_name_H-M_alt        'P 42/n :2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2022-05-02
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-05-02 deposited with the CCDC.	2022-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   37.1760(2)
_cell_length_b                   37.1760(2)
_cell_length_c                   11.96640(10)
_cell_measurement_reflns_used    94703
_cell_measurement_temperature    120.15
_cell_measurement_theta_max      30.3920
_cell_measurement_theta_min      3.6250
_cell_volume                     16538.22(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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      5.00  68.00   0.30   30.00    --   14.65-124.00 -23.00  210
  2  \w     20.00  83.00   0.30   30.00    --   14.65-148.00 171.00  210
  3  \w    -43.00  19.10   0.30   30.00    --  -13.08  77.00-150.00  207
  4  \w    -21.00   7.20   0.30   30.00    --  -13.08  77.00-120.00   94
  5  \w    -42.00  10.20   0.30   30.00    --  -13.08 -77.00 -30.00  174
  6  \w    -44.00 -17.90   0.30   30.00    --   14.65 -38.00 120.00   87
  7  \w     58.00  85.00   0.30   30.00    --   14.65 178.00-150.00   90
  8  \w     38.00  87.20   0.30   30.00    --   14.65-178.00 120.00  164
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0053456000
_diffrn_orient_matrix_UB_12      0.0182744000
_diffrn_orient_matrix_UB_13      -0.0036556000
_diffrn_orient_matrix_UB_21      -0.0159544000
_diffrn_orient_matrix_UB_22      0.0052478000
_diffrn_orient_matrix_UB_23      0.0281700000
_diffrn_orient_matrix_UB_31      0.0090084000
_diffrn_orient_matrix_UB_32      -0.0015669000
_diffrn_orient_matrix_UB_33      0.0520273000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0499
_diffrn_reflns_av_unetI/netI     0.0302
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            152030
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.732
_diffrn_reflns_theta_min         3.195
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.841
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.308
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light blue'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.359
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             6928
_exptl_crystal_preparation
'NiCl2 and ligand in methanol has been refluxed for a day and the clear solution was layered with acetone.'
_exptl_crystal_recrystallization_method
'The material was recrystallised from Acetone by solvent layering'
_exptl_crystal_size_max          0.851
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.089
_refine_diff_density_max         1.234
_refine_diff_density_min         -0.615
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.172
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     820
_refine_ls_number_reflns         17519
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.172
_refine_ls_R_factor_all          0.0634
_refine_ls_R_factor_gt           0.0570
_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^)+(0.0423P)^2^+72.7487P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1273
_refine_ls_wR_factor_ref         0.1300
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15915
_reflns_number_total             17519
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03445j2.cif
_cod_data_source_block           ea-416_acetone_auto
_cod_original_cell_volume        16538.2(2)
_cod_original_sg_symbol_H-M      'P 42/n'
_cod_database_code               7130321
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C87 H140 Cl14 N24 Ni14 O34'
_chemical_oxdiff_usercomment     '@ 120 K ABG-0549'
_shelx_estimated_absorpt_t_max   0.853
_shelx_estimated_absorpt_t_min   0.303
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H) groups, All O(H,H)
  groups
2. Shared sites
{O15, O15A}
3. Restrained distances
 O15-H15
 0.87 with sigma of 0.01
 Ni5-H15
 2.623747 with sigma of 0.02
 C42-C44 \\sim C42A-C44
 with sigma of 0.02
 O17-C44 \\sim O17A-C44
 with sigma of 0.04
 O17-C43 \\sim O17A-C43
 with sigma of 0.04
 C42-C43 \\sim C42A-C43
 with sigma of 0.02
 O17-C42 \\sim O17A-C42A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(O15) = Uanis(O15A)
5. Rigid body (RIGU) restrains
 O17A, C42A, C43, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O17A)=Sof(C42A)=Sof(H43D)=Sof(H43E)=Sof(H43F)=Sof(H44D)=Sof(H44E)=
 Sof(H44F)=1-FVAR(1)
 Sof(O17)=Sof(C42)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(H44A)=Sof(H44B)=Sof(H44C)=
 FVAR(1)
 Fixed Sof: O15(0.5) H15(0.5) C38(0.5) H38A(0.5) H38B(0.5) H38C(0.5) O15A(0.5)
 H15A(0.5) H15B(0.5)
7.a Rotating group:
 O15A(H15A,H15B)
7.b Me refined with riding coordinates:
 C43(H43A,H43B,H43C), C43(H43D,H43E,H43F), C44(H44A,H44B,H44C), C44(H44D,H44E,
 H44F)
7.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N4(H4), N6(H6), N8(H8), N10(H10), N12(H12), C2(H2A), C7(H7),
 C12(H12A), C17(H17), C22(H22), C27(H27), C31(H31), C32(H32), C33(H33),
 C34(H34), C35(H35), C36(H36), C37(H37)
7.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C9(H9A,H9B,H9C),
 C10(H10A,H10B,H10C), C14(H14A,H14B,H14C), C15(H15C,H15D,H15E), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C29(H29A,
 H29B,H29C), C30(H30A,H30B,H30C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
7.e Idealised tetrahedral OH refined as rotating group:
 O15(H15)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 268 electrons were 
found in a volume of 4122\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
2[C3H6O] per Formula Unit 
which account for 256 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              75645
_shelx_hkl_checksum              51009
_shelx_fab_checksum              28606
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_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 1.270
_oxdiff_exptl_absorpt_empirical_full_min 0.770