Unmasking the constitution and bonding of the proposed lithium nickelate “Li3NiPh3(solv)3”: Revealing the hidden C6H4 ligand
Somerville, Rosie J.; Campos, Jesús; Carmona, Ernesto; Grabowsky, Simon; Malaspina, Lorraine A.; Balcells, David; Hevia, Eva; Nova, Ainara; Pérez-Jiménez, Marina; Borys, Andryj M.; Chemical Science  (2022) –; doi:10.1039/D2SC01244H

data_1566781
_publ_section_title
;
 Unmasking the constitution and bonding of the proposed lithium nickelate
 &#x201C;Li3NiPh3(solv)3&#x201D;: Revealing the hidden C6H4 ligand
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01244H
_journal_year                    2022
_chemical_formula_moiety         'C80 H126 Na6 Ni2 O6'
_chemical_formula_sum            'C80 H126 Na6 Ni2 O6'
_chemical_formula_weight         1439.13
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      15
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-10T17:48:57-00:00
_audit_update_record
;
2021-12-08 deposited with the CCDC.	2022-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.7306(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.45144(13)
_cell_length_b                   17.82545(10)
_cell_length_c                   22.25202(14)
_cell_measurement_reflns_used    72089
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      79.496
_cell_measurement_theta_min      3.296
_cell_volume                     8009.22(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1
_diffrn_measured_fraction_theta_max 1
_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    -94.00  -8.00   0.50    0.35    --  -23.00 -57.00 -67.00  172
  2  \w    -38.00  50.00   0.50    0.35    --  -23.00  57.00  74.00  176
  3  \w    -23.00  63.00   0.50    0.35    --   47.95 -57.00 -67.00  172
  4  \w     33.00 119.00   0.50    0.35    --   47.95  57.00  74.00  172
  5  \w     98.00 177.00   0.50    2.00    --  113.25  57.00  74.00  158
  6  \w    -95.00   0.00   0.50    0.35    --  -23.00 -77.00-180.00  190
  7  \w    -70.00 -12.00   0.50    0.35    --  -23.00 125.00 120.00  116
  8  \w    -95.00 -10.00   0.50    0.35    --  -23.00 -45.00 -30.00  170
  9  \w    -70.00 -12.00   0.50    0.35    --  -23.00 125.00  90.00  116
 10  \w     25.00 120.00   0.50    0.35    --   47.95  77.00  30.00  190
 11  \w    -26.00  23.00   0.50    0.35    --   47.95 -19.00-180.00   98
 12  \w     42.00 141.00   0.50    2.00    --  113.25 -88.00  52.49  198
 13  \w     42.00  68.00   0.50    2.00    --  113.25 -61.00  90.00   52
 14  \w     42.00 106.00   0.50    2.00    --  113.25 -94.00 -30.00  128
 15  \w     98.00 177.00   0.50    2.00    --  113.25  58.00  42.51  158
 16  \w     91.00 177.00   0.50    2.00    --  113.25  77.00-180.00  172
 17  \w     97.00 177.00   0.50    2.00    --  113.25  61.00 -90.00  160
 18  \w     42.00 105.00   0.50    2.00    --  113.25 -92.00-104.65  126
 19  \w    101.00 177.00   0.50    2.00    --  113.25  45.00  30.00  152
 20  \w     97.00 177.00   0.50    2.00    --  113.25  61.00   0.00  160
 21  \w     97.00 177.00   0.50    2.00    --  113.25  61.00 120.00  160
 22  \w     42.00 106.00   0.50    2.00    --  113.25 -94.00-150.00  128
 23  \w    101.00 177.00   0.50    2.00    --  113.25  31.00  21.05  152
 24  \w    100.00 177.00   0.50    2.00    --  113.25  48.00 -34.62  154
 25  \w     42.00 102.00   0.50    2.00    --  113.25 -77.00  60.00  120
 26  \w     97.00 177.00   0.50    2.00    --  113.25  61.00-150.00  160
 27  \w    101.00 177.00   0.50    2.00    --  113.25  45.00-180.00  152
 28  \w     97.00 177.00   0.50    2.00    --  113.25  61.00  30.00  160
 29  \w     91.00 177.00   0.50    2.00    --  113.25  77.00 -30.00  172
 30  \w     42.00 102.00   0.50    2.00    --  113.25 -77.00 150.00  120
 31  \w     93.00 177.00   0.50    2.00    --  113.25  71.00-107.31  168
 32  \w     42.00  68.00   0.50    2.00    --  113.25 -61.00 120.00   52
 33  \w    101.00 177.00   0.50    2.00    --  113.25  30.00  30.00  152
 34  \w     42.00 102.00   0.50    2.00    --  113.25 -77.00-150.00  120
 35  \w     42.00  68.00   0.50    2.00    --  113.25 -61.00 150.00   52
 36  \w    101.00 177.00   0.50    2.00    --  113.25  43.00  36.70  152
 37  \w     93.00 177.00   0.50    2.00    --  113.25  71.00 -76.17  168
 38  \w     42.00  68.00   0.50    2.00    --  113.25 -61.00 -60.00   52
 39  \w     96.00 177.00   0.50    2.00    --  113.25  64.00  47.77  162
 40  \w     42.00 106.00   0.50    2.00    --  113.25 -94.00-120.00  128
 41  \w    100.00 177.00   0.50    2.00    --  113.25  15.00 -90.00  154
 42  \w     42.00  68.00   0.50    2.00    --  113.25 -61.00  60.00   52
 43  \w     42.00 102.00   0.50    2.00    --  113.25 -77.00   0.00  120
 44  \w     42.00 102.00   0.50    2.00    --  113.25 -77.00 120.00  120
 45  \w    101.00 177.00   0.50    2.00    --  113.25  45.00  60.00  152
 46  \w    101.00 177.00   0.50    2.00    --  113.25  30.00  60.00  152
 47  \w    106.00 177.00   0.50    2.00    --  113.25 102.00 -54.24  142
 48  \w    -70.00 -12.00   0.50    0.35    --  -23.00 125.00 -60.00  116
 49  \w     25.00 120.00   0.50    0.35    --   47.95  77.00 -30.00  190
 50  \w     -1.00  81.00   0.50    0.35    --   47.95 -99.00 -60.00  164
 51  \w     25.00 120.00   0.50    0.35    --   47.95  77.00 120.00  190
 52  \w     25.00 120.00   0.50    0.35    --   47.95  77.00 -60.00  190
 53  \w     25.00 120.00   0.50    0.35    --   47.95  77.00 150.00  190
 54  \w     25.00 120.00   0.50    0.35    --   47.95  77.00  90.00  190
 55  \w     -1.00  81.00   0.50    0.35    --   47.95 -99.00 120.00  164
 56  \w     25.00 120.00   0.50    0.35    --   47.95  77.00-120.00  190
 57  \w     25.00 120.00   0.50    0.35    --   47.95  77.00   0.00  190
 58  \w     36.00 121.00   0.50    0.35    --   47.95  38.00 -30.00  170
 59  \w     25.00 120.00   0.50    0.35    --   47.95  77.00-150.00  190
 60  \w     42.00  68.00   0.50    2.00    --  113.25 -61.00 -90.00   52
 61  \w     95.00 177.00   0.50    2.00    --  113.25  67.00 131.85  164
;
_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      0.0386938
_diffrn_orient_matrix_UB_12      -0.0582229
_diffrn_orient_matrix_UB_13      0.0497782
_diffrn_orient_matrix_UB_21      -0.0656476
_diffrn_orient_matrix_UB_22      -0.0315972
_diffrn_orient_matrix_UB_23      0.003143
_diffrn_orient_matrix_UB_31      -0.0032203
_diffrn_orient_matrix_UB_32      -0.0555127
_diffrn_orient_matrix_UB_33      -0.0540805
_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  0.0467
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            113505
_diffrn_reflns_point_group_measured_fraction_full 1
_diffrn_reflns_point_group_measured_fraction_max 1
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.498
_diffrn_reflns_theta_min         3.307
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.271
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.43875
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.194
_exptl_crystal_description       block
_exptl_crystal_F_000             3104
_exptl_crystal_size_max          0.225
_exptl_crystal_size_mid          0.205
_exptl_crystal_size_min          0.135
_refine_diff_density_max         0.659
_refine_diff_density_min         -0.527
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     524
_refine_ls_number_reflns         8086
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0494
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0672P)^2^+12.1959P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1357
_refine_ls_wR_factor_ref         0.1369
_reflns_Friedel_coverage         0
_reflns_number_gt                7681
_reflns_number_total             8086
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01244h5.cif
_cod_data_source_block           21EH115_AMB-502
_cod_original_cell_volume        8009.21(9)
_cod_database_code               1566781
_shelx_estimated_absorpt_t_min   0.763
_shelx_estimated_absorpt_t_max   0.847
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.449
_oxdiff_exptl_absorpt_empirical_full_min 0.602
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
        1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        2. Restrained distances
 C37-C36 \\sim C37A-C36A
 with sigma of 0.002
        3. Rigid bond restraints
 C36, C37
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O3A, C38A, C39A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
        4. Uiso/Uaniso restraints and constraints
Uanis(C34) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of 0.01 and sigma for
        terminal atoms of 0.02
        5. Others
 Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(C40A)=Sof(H40B)=Sof(H40C)=Sof(H40A)=
 Sof(O3A)=Sof(C39A)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 1-FVAR(1)
 Sof(O3)=Sof(C38)=Sof(H38C)=Sof(H38D)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=
 Sof(C39)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40)=Sof(H40D)=Sof(H40E)=FVAR(1)
 Sof(O2A)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(C37A)=Sof(H37D)=Sof(H37E)=
 Sof(H37F)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C35A)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=1-FVAR(2)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=
 Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(O2)=Sof(C34)=Sof(H34C)=Sof(H34D)=FVAR(2)
        6.a Ternary CH refined with riding coordinates:
 C14(H14), C13(H13), C29(H29), C22(H22), C28(H28), C25(H25), C26(H26)
        6.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C20(H20A,H20B), C16(H16A,H16B), C30(H30A,H30B), C19(H19A,
 H19B), C27(H27A,H27B), C23(H23A,H23B), C32(H32A,H32B), C38A(H38A,H38B),
 C34A(H34A,H34B), C38(H38C,H38D), C24(H24A,H24B), C36(H36A,H36B), C21(H21A,
 H21B), C40(H40D,H40E), C36A(H36C,H36D), C34(H34C,H34D)
        6.c Me refined with riding coordinates:
 C35(H35A,H35B,H35C), C35A(H35D,H35E,H35F)
        6.d Aromatic/amide H refined with riding coordinates:
 C12(H12), C6(H6), C8(H8), C2(H2), C5(H5), C11(H11), C4(H4), C3(H3), C9(H9),
 C10(H10), C18(H18), C17(H17)
        6.e Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C40A(H40B,H40C,H40A), C41(H41A,H41B,
 H41C), C39A(H39A,H39B,H39C), C37(H37A,H37B,H37C), C37A(H37D,H37E,H37F),
 C39(H39D,H39E,H39F)
;
_shelx_res_checksum              77094
_shelx_hkl_checksum              36738