Ferromagnetically coupled tetranuclear Ni(ii)-2-oxy-aceto- or benzo-phenonate complexes
Haque, Imdadul; Enamullah, Mohammed; Jhumur, Nisat Taslum; Sidhu, Baldeep K.; Herbert, David E.; Haj Hassani Sohi, Takin; Havlíček, Lubomír; Nemec, Ivan; Janiak, Christoph; RSC Advances 15 (2025) 4250–4261; doi:10.1039/D4RA08700C

data_7249922
_publ_section_title
;
 Ferromagnetically coupled tetranuclear Ni(ii)-2-oxy-aceto- or
 benzo-phenonate complexes
;
_journal_issue                   6
_journal_name_full               'RSC Advances'
_journal_page_first              4250
_journal_page_last               4261
_journal_paper_doi               10.1039/D4RA08700C
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C40 H56 Ni4 O16'
_chemical_formula_sum            'C40 H56 Ni4 O16'
_chemical_formula_weight         1027.68
_chemical_name_common
tetrakis-[(\m~3~-methanolato-\k^3^O:O:O)(methanol-\kO)(2-oxyacetophenone-\k^2^O,O')nickel(II)]
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-30
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-07-01 deposited with the CCDC.	2025-01-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.2175(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.08705(9)
_cell_length_b                   15.15100(7)
_cell_length_c                   15.82527(8)
_cell_measurement_reflns_used    95263
_cell_measurement_temperature    298.60(14)
_cell_measurement_theta_max      76.1070
_cell_measurement_theta_min      2.3110
_cell_volume                     4557.51(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      298.60(14)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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   -109.00 -76.00   0.50    0.16    --  -47.91 -54.00 112.00   66
  2  \w    -23.00  48.00   0.50    0.16    --   47.91 -54.00 112.00  142
  3  \w     53.00  80.00   0.50    0.16    --   47.91  54.00-104.00   54
  4  \w     94.00 119.00   0.50    0.16    --   47.91  54.00-104.00   50
  5  \w    -67.00 -41.00   0.50    0.62    --  -84.25  54.00-104.00   52
  6  \w   -134.00 -94.00   0.50    0.62    --  -84.25 -54.00 112.00   80
  7  \w     93.00 175.00   0.50    0.62    --  105.75  54.00-104.00  164
  8  \w    -20.00  18.00   0.50    0.16    --   12.00 101.00-124.30   76
  9  \w     -9.00  17.00   0.50    0.16    --   20.00 101.00 -34.50   52
 10  \w     -6.00  22.00   0.50    0.16    --   24.00  98.00 176.46   56
 11  \w      2.00  27.00   0.50    0.16    --   32.00  97.00  67.62   50
 12  \w     17.00  42.00   0.50    0.16    --   44.00  88.00  90.18   50
 13  \w     15.00  40.00   0.50    0.16    --   44.00  92.00  17.54   50
 14  \w     16.00  41.00   0.50    0.16    --   44.00  91.00 158.76   50
 15  \w     17.00  42.00   0.50    0.16    --   44.00  88.00 -75.21   50
 16  \w     17.00  42.00   0.50    0.16    --   44.00  89.00-162.16   50
 17  \w   -117.00 -70.00   0.50    0.16    --  -47.91 -77.00 -30.00   94
 18  \w    -63.00 -26.00   0.50    0.16    --  -47.91 -77.00 120.00   74
 19  \w    -52.00 -26.00   0.50    0.16    --  -47.91 -77.00-150.00   52
 20  \w   -119.00 -48.00   0.50    0.16    --  -47.91-178.00 -60.00  142
 21  \w    -59.00  18.00   0.50    0.16    --  -47.91  54.00-104.00  154
 22  \w   -101.00 -75.00   0.50    0.16    --  -47.91 -77.00-150.00   52
 23  \w    -58.00 -28.00   0.50    0.16    --  -47.91 -77.00 -30.00   60
 24  \w     48.00  85.00   0.50    0.16    --   47.91  19.00  30.00   74
 25  \w     39.00 110.00   0.50    0.16    --   47.91  19.00-180.00  142
 26  \w     38.00  73.00   0.50    0.16    --   47.91  19.00 120.00   70
 27  \w     89.00 116.00   0.50    0.16    --   47.91  19.00  30.00   54
 28  \w    -74.00 -34.00   0.50    0.16    --  -56.00 -77.00-171.43   80
 29  \w   -127.00-102.00   0.50    0.16    --  -56.00 -77.00  60.27   50
 30  \w    -65.00 -34.00   0.50    0.16    --  -56.00 -77.00  60.27   62
 31  \w   -126.00 -81.00   0.50    0.16    --  -56.00 -77.00-171.43   90
 32  \w    -79.00 -35.00   0.50    0.16    --  -56.00 -74.00-133.84   88
 33  \w    -60.00 -35.00   0.50    0.16    --  -56.00 -76.00  17.61   50
 34  \w   -120.00 -94.00   0.50    0.16    --  -56.00 -76.00  17.61   52
 35  \w    -64.00 -39.00   0.50    0.16    --  -60.00 -75.00 -85.45   50
 36  \w    -64.00 -38.00   0.50    0.16    --  -60.00 -77.00 -68.15   52
 37  \w    -73.00 -38.00   0.50    0.16    --  -60.00 -77.00 -38.47   70
 38  \w     39.00  84.00   0.50    0.16    --   60.00  75.00 155.20   90
 39  \w   -128.00-102.00   0.50    0.16    --  -64.00 -77.00 166.79   52
 40  \w    -68.00 -42.00   0.50    0.16    --  -64.00 -77.00 166.79   52
 41  \w    -69.00 -43.00   0.50    0.16    --  -64.00 -74.00 -91.78   52
 42  \w    -77.00 -45.00   0.50    0.16    --  -64.00 -69.00 102.19   64
 43  \w    -71.00 -46.00   0.50    0.16    --  -68.00 -77.00 107.78   50
 44  \w    -72.00 -47.00   0.50    0.16    --  -68.00 -75.00-161.13   50
 45  \w    -72.00 -47.00   0.50    0.16    --  -68.00 -76.00  15.91   50
 46  \w    -75.00 -49.00   0.50    0.16    --  -68.00 -75.00  61.84   52
 47  \w    -71.00 -46.00   0.50    0.16    --  -68.00 -77.00 -10.72   50
 48  \w    -77.00 -50.00   0.50    0.16    --  -72.00 -77.00-152.73   54
 49  \w    -76.00 -51.00   0.50    0.16    --  -72.00 -76.00 153.06   50
 50  \w    -80.00 -51.00   0.50    0.16    --  -72.00 -75.00-102.72   58
 51  \w    -82.00 -51.00   0.50    0.16    --  -72.00 -75.00 178.57   62
 52  \w    -81.00 -51.00   0.50    0.16    --  -72.00 -74.00-139.93   60
 53  \w    -90.00 -55.00   0.50    0.16    --  -76.00 -76.00 -48.00   70
 54  \w    -81.00 -55.00   0.50    0.16    --  -76.00 -74.00  99.11   52
 55  \w    -81.00 -55.00   0.50    0.16    --  -76.00 -76.00  49.42   52
 56  \w    -81.00 -55.00   0.50    0.16    --  -76.00 -76.00-113.53   52
 57  \w    -83.00 -58.00   0.50    0.62    --  -80.00 -77.00 151.29   50
 58  \w    -85.00 -59.00   0.50    0.62    --  -80.00 -76.00 -62.57   52
 59  \w    -90.00 -64.00   0.50    0.62    --  -84.25 -74.00-109.48   52
 60  \w   -153.00-116.00   0.50    0.62    --  -84.25 -77.00-124.76   74
 61  \w   -102.00 -64.00   0.50    0.62    --  -84.25 -76.00  76.67   76
 62  \w    -90.00 -62.00   0.50    0.62    --  -84.25 -77.00  60.00   56
 63  \w   -125.00 -64.00   0.50    0.62    --  -84.25 -72.00-163.46  122
 64  \w    -90.00 -63.00   0.50    0.62    --  -84.25 -76.00-136.77   54
 65  \w   -152.00-124.00   0.50    0.62    --  -84.25 -76.00-136.77   56
 66  \w   -153.00-127.00   0.50    0.62    --  -84.25 -76.00  76.67   52
 67  \w    -90.00 -64.00   0.50    0.62    --  -84.25 -73.00  91.45   52
 68  \w    -98.00 -63.00   0.50    0.62    --  -84.25 -76.00 127.35   70
 69  \w   -153.00 -68.00   0.50    0.62    --  -84.25 -65.00  95.83  170
 70  \w    -92.00 -63.00   0.50    0.62    --  -84.25 -76.00 174.65   58
 71  \w   -141.00-115.00   0.50    0.62    --  -84.25 -73.00  91.45   52
 72  \w    -91.00 -66.00   0.50    0.62    --  -84.25 -69.00-178.92   50
 73  \w   -155.00-113.00   0.50    0.62    --  -84.25 -76.00 127.35   84
 74  \w   -100.00 -64.00   0.50    0.62    --  -84.25 -74.00  16.95   72
 75  \w    -91.00 -65.00   0.50    0.62    --  -84.25 -73.00 -15.46   52
 76  \w   -114.00 -62.00   0.50    0.62    --  -84.25 -77.00 150.00  104
 77  \w    -89.00 -63.00   0.50    0.62    --  -84.25 -76.00  38.87   52
 78  \w   -150.00-119.00   0.50    0.62    --  -84.25 -76.00  38.87   62
 79  \w   -105.00 -64.00   0.50    0.62    --  -84.25 -77.00  90.00   82
 80  \w   -156.00-121.00   0.50    0.62    --  -84.25 -77.00  90.00   70
 81  \w    -87.00 -62.00   0.50    0.62    --  -84.25 -77.00-180.00   50
 82  \w   -145.00-108.00   0.50    0.62    --  -84.25 -77.00-180.00   74
 83  \w    -90.00 -64.00   0.50    0.62    --  -84.25 -75.00 -87.59   52
 84  \w   -123.00 -64.00   0.50    0.62    --  -84.25 -75.00   7.81  118
 85  \w   -147.00-118.00   0.50    0.62    --  -84.25 -77.00  60.00   58
 86  \w   -155.00-115.00   0.50    0.62    --  -84.25 -75.00 -87.59   80
 87  \w   -101.00 -62.00   0.50    0.62    --  -84.25 -77.00   0.00   78
 88  \w   -100.00 -64.00   0.50    0.62    --  -84.25 -72.00 -53.10   72
 89  \w   -139.00-113.00   0.50    0.62    --  -84.25 -77.00   0.00   52
 90  \w    -89.00 -64.00   0.50    0.62    --  -84.25 -72.00 -77.43   50
 91  \w   -141.00-116.00   0.50    0.62    --  -84.25 -72.00 -77.43   50
 92  \w    -88.00 -62.00   0.50    0.62    --  -84.25 -77.00-124.76   52
 93  \w   -156.00-125.00   0.50    0.62    --  -84.25 -74.00  16.95   62
 94  \w    -87.00 -62.00   0.50    0.62    --  -84.25 -77.00 -30.00   50
 95  \w   -115.00 -90.00   0.50    0.62    --  -84.25 -77.00 -30.00   50
 96  \w    -88.00 -63.00   0.50    0.62    --  -84.25 -75.00 -21.30   50
 97  \w     87.00 177.00   0.50    0.62    --  105.75  77.00 120.00  180
 98  \w     35.00  61.00   0.50    0.62    --  105.75 -57.00  30.00   52
 99  \w     38.00 102.00   0.50    0.62    --  105.75 -99.00 -90.00  128
100  \w     86.00 175.00   0.50    0.62    --  105.75  77.00 -60.00  178
101  \w     37.00 102.00   0.50    0.62    --  105.75 -99.00-180.00  130
102  \w     68.00 105.00   0.50    0.62    --  105.75 -99.00  60.00   74
103  \w     36.00  65.00   0.50    0.62    --  105.75 -99.00  60.00   58
104  \w     42.00 104.00   0.50    0.62    --  105.75 -99.00  30.00  124
105  \w     37.00 103.00   0.50    0.62    --  105.75 -99.00 120.00  132
106  \w     36.00 106.00   0.50    0.62    --  105.75 -99.00   0.00  140
107  \w     37.00 111.00   0.50    0.62    --  105.75-125.00 120.00  148
108  \w     39.00 109.00   0.50    0.62    --  105.75-115.00 166.34  140
109  \w    150.00 175.00   0.50    0.62    --  105.75  77.00  30.00   50
110  \w     87.00 126.00   0.50    0.62    --  105.75  77.00  30.00   78
111  \w     87.00 172.00   0.50    0.62    --  105.75  77.00 -90.00  170
112  \w     77.00 110.00   0.50    0.62    --  105.75-125.00   0.00   66
113  \w     97.00 163.00   0.50    0.62    --  105.75  19.00   0.00  132
114  \w     37.00  72.00   0.50    0.62    --  105.75-125.00   0.00   70
115  \w     96.00 176.00   0.50    0.62    --  105.75  38.00-120.00  160
116  \w    102.00 178.00   0.50    0.62    --  105.75  38.00-180.00  152
117  \w     35.00  60.00   0.50    0.62    --  105.75 -57.00   0.00   50
118  \w     37.00  91.00   0.50    0.62    --  105.75 -99.00-150.00  108
119  \w     36.00 103.00   0.50    0.62    --  105.75 -99.00 -60.00  134
120  \w     97.00 139.00   0.50    0.62    --  105.75  57.00  30.00   84
121  \w    112.00 176.00   0.50    0.62    --  105.75  38.00  90.00  128
122  \w    100.00 140.00   0.50    0.62    --  105.75  19.00-120.00   80
123  \w     38.00 109.00   0.50    0.62    --  105.75-112.00 -86.94  142
124  \w     35.00  60.00   0.50    0.62    --  105.75 -57.00-180.00   50
125  \w     35.00  60.00   0.50    0.62    --  105.75 -57.00 -90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0522528000
_diffrn_orient_matrix_UB_12      -0.0738712000
_diffrn_orient_matrix_UB_13      -0.0174614000
_diffrn_orient_matrix_UB_21      0.0044366000
_diffrn_orient_matrix_UB_22      0.0360773000
_diffrn_orient_matrix_UB_23      -0.0903745000
_diffrn_orient_matrix_UB_31      0.0617907000
_diffrn_orient_matrix_UB_32      0.0598565000
_diffrn_orient_matrix_UB_33      0.0328896000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0410
_diffrn_reflns_av_unetI/netI     0.0129
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            160640
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.437
_diffrn_reflns_theta_min         2.324
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.417
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.538
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
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            'clear green'
_exptl_crystal_density_diffrn    1.498
_exptl_crystal_description       block
_exptl_crystal_F_000             2144
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane/methanol'
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.324
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     576
_refine_ls_number_reflns         9486
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0515P)^2^+1.4514P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0967
_refine_ls_wR_factor_ref         0.0980
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8883
_reflns_number_total             9486
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra08700c2.cif
_cod_data_source_block           nil104_2
_cod_database_code               7249922
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C40H56Ni4O16
_shelx_estimated_absorpt_t_max   0.744
_shelx_estimated_absorpt_t_min   0.521
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 O7-H7
 1 with sigma of 0.02
 O10-C32A \\sim O10-C32B
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 O7, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O16, C13
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Others
 Sof(C32B)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7A), C15(H15), C16(H16A), C17(H17), C18(H18),
 C25(H25), C26(H26), C27(H27), C28(H28), C34(H34), C35(H35), C36(H36), C37(H37)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C32A(H32A,H32B,H32C),
 C32B(H32D,H32E,H32F), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              10569
_shelx_hkl_checksum              23334
_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 2.401
_oxdiff_exptl_absorpt_empirical_full_min 0.743