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_1566776
_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         'C56 H71.75 Li5 Ni2 O5'
_chemical_formula_sum            'C56 H71.75 Li5 Ni2 O5'
_chemical_formula_weight         977
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_cell_setting           monoclinic
_symmetry_Int_Tables_number      14
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-31T10:20:59-00:00
_audit_update_record
;
2021-12-08 deposited with the CCDC.	2022-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.7134(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.24036(9)
_cell_length_b                   14.66026(7)
_cell_length_c                   22.76116(11)
_cell_measurement_reflns_used    59812
_cell_measurement_temperature    173.01(10)
_cell_measurement_theta_max      79.479
_cell_measurement_theta_min      3.602
_cell_volume                     5306.30(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (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      173.01(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    -62.00  -1.00   0.50    1.00    --  -23.00 110.00  69.00  122
  2  \w     23.00  88.00   0.50    1.00    --   47.95-110.00 -25.00  130
  3  \w     42.00 108.00   0.50    9.00    --  113.25-110.00 -25.00  132
  4  \w    -70.00 -12.00   0.50    1.00    --  -23.00 125.00-150.00  116
  5  \w    -70.00 -12.00   0.50    1.00    --  -23.00 125.00 -60.00  116
  6  \w    -39.00  50.00   0.50    1.00    --  -23.00  61.00  90.00  178
  7  \w    -70.00 -12.00   0.50    1.00    --  -23.00 125.00-120.00  116
  8  \w    -95.00 -10.00   0.50    1.00    --  -23.00 -45.00 -60.00  170
  9  \w     -1.00  81.00   0.50    1.00    --   47.95 -99.00-150.00  164
 10  \w    -23.00  63.00   0.50    1.00    --   47.95 -57.00-150.00  172
 11  \w     33.00 119.00   0.50    1.00    --   47.95  57.00-180.00  172
 12  \w    -26.00  23.00   0.50    1.00    --   47.95 -19.00-120.00   98
 13  \w    -26.00  23.00   0.50    1.00    --   47.95 -19.00 -60.00   98
 14  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00 -90.00  128
 15  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00 120.00  128
 16  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00   0.00  128
 17  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00  30.00  128
 18  \w     97.00 177.00   0.50    9.00    --  113.25  61.00-180.00  160
 19  \w     42.00  68.00   0.50    9.00    --  113.25 -61.00   0.00   52
 20  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00  90.00  128
 21  \w     42.00 108.00   0.50    9.00    --  113.25-106.00-145.13  132
 22  \w     91.00 177.00   0.50    9.00    --  113.25  76.00 137.61  172
 23  \w     42.00  68.00   0.50    9.00    --  113.25 -61.00  60.00   52
 24  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00 -60.00  128
 25  \w     42.00 102.00   0.50    9.00    --  113.25 -77.00-150.00  120
 26  \w     42.00 102.00   0.50    9.00    --  113.25 -77.00  60.00  120
 27  \w     97.00 177.00   0.50    9.00    --  113.25  61.00 -90.00  160
 28  \w     42.00  68.00   0.50    9.00    --  113.25 -61.00 -60.00   52
 29  \w     42.00 102.00   0.50    9.00    --  113.25 -77.00 120.00  120
 30  \w     42.00 102.00   0.50    9.00    --  113.25 -77.00  30.00  120
 31  \w    100.00 177.00   0.50    9.00    --  113.25  15.00 150.00  154
 32  \w     42.00  68.00   0.50    9.00    --  113.25 -61.00 -90.00   52
 33  \w    100.00 177.00   0.50    9.00    --  113.25  15.00-150.00  154
 34  \w    101.00 177.00   0.50    9.00    --  113.25  30.00  90.00  152
 35  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00 -30.00  128
 36  \w    100.00 177.00   0.50    9.00    --  113.25  15.00   0.00  154
 37  \w     92.00 177.00   0.50    9.00    --  113.25  73.00 113.04  170
 38  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00  60.00  128
 39  \w     97.00 177.00   0.50    9.00    --  113.25  61.00  30.00  160
 40  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00 150.00  128
 41  \w    101.00 177.00   0.50    9.00    --  113.25  45.00-150.00  152
 42  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00-150.00  128
 43  \w     42.00  68.00   0.50    9.00    --  113.25 -61.00  90.00   52
 44  \w     42.00 106.00   0.50    9.00    --  113.25 -94.00-120.00  128
 45  \w    101.00 177.00   0.50    9.00    --  113.25  45.00 -30.00  152
 46  \w     42.00  68.00   0.50    9.00    --  113.25 -61.00 -30.00   52
 47  \w    100.00 177.00   0.50    9.00    --  113.25  15.00  60.00  154
 48  \w    106.00 177.00   0.50    9.00    --  113.25  96.00  48.26  142
 49  \w    101.00 177.00   0.50    9.00    --  113.25  30.00-120.00  152
;
_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      -0.0410487
_diffrn_orient_matrix_UB_12      -0.0950374
_diffrn_orient_matrix_UB_13      -0.0022704
_diffrn_orient_matrix_UB_21      0.0817441
_diffrn_orient_matrix_UB_22      -0.0390682
_diffrn_orient_matrix_UB_23      0.0380769
_diffrn_orient_matrix_UB_31      -0.0319243
_diffrn_orient_matrix_UB_32      0.0220007
_diffrn_orient_matrix_UB_33      0.0576562
_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  0.045
_diffrn_reflns_av_unetI/netI     0.0595
_diffrn_reflns_Laue_measured_fraction_full 1
_diffrn_reflns_Laue_measured_fraction_max 1
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            102036
_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         69.137
_diffrn_reflns_theta_min         2.779
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.217
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.52292
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
        CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
        Empirical absorption correction using spherical harmonics,
        implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.223
_exptl_crystal_description       plate
_exptl_crystal_F_000             2075
_exptl_crystal_size_max          0.243
_exptl_crystal_size_mid          0.092
_exptl_crystal_size_min          0.071
_refine_diff_density_max         0.644
_refine_diff_density_min         -0.478
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     757
_refine_ls_number_reflns         9893
_refine_ls_number_restraints     100
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.041
_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^)+(0.0681P)^2^+2.4308P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1167
_refine_ls_wR_factor_ref         0.1203
_reflns_Friedel_coverage         0
_reflns_number_gt                9013
_reflns_number_total             9893
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01244h5.cif
_cod_data_source_block           21EH168_AMB-609
_cod_database_code               1566776
_shelx_estimated_absorpt_t_min   0.756
_shelx_estimated_absorpt_t_max   0.919
_oxdiff_exptl_absorpt_empirical_details
;
        Empirical correction (ABSPACK) includes:
        - Absorption correction using spherical harmonics
        - Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.225
_oxdiff_exptl_absorpt_empirical_full_min 0.676
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
        2. Rigid bond restraints
 O1, C39A, C39, C38, C37
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 O1, C40, C40A, C37A, C38A
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 C22, C23, C21, C20, C19, C24
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O2A, C44A, C43, C41A, C42A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C15, C16, C17, C18, C14, C13
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C43, C42, O2, C41, C44
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
        3. Uiso/Uaniso restraints and constraints
Uanis(C39A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.02
Uanis(O3A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C48A) \\sim Ueq, Uanis(C47A) \\sim Ueq, Uanis(C47) \\sim Ueq: with sigma
        of 0.01 and sigma for terminal atoms of 0.02
Uanis(C38) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C39) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
        4. Others
 Sof(H45C)=Sof(H45D)=Sof(C46A)=Sof(H46C)=Sof(H46D)=Sof(C47A)=Sof(H47C)=
 Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=Sof(O3A)=1-FVAR(1)
 Sof(O3)=Sof(H45A)=Sof(H45B)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C47)=Sof(H47A)=
 Sof(H47B)=Sof(C46)=Sof(H46A)=Sof(H46B)=FVAR(1)
 Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(C42A)=
 Sof(H42C)=Sof(H42D)=Sof(H42E)=Sof(O2A)=Sof(C44A)=Sof(H44C)=Sof(H44D)=1-FVAR(2)
 Sof(O2)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H43D)=Sof(H43E)=Sof(C42)=Sof(H42A)=
 Sof(H42B)=Sof(C41)=Sof(H41A)=Sof(H41B)=FVAR(2)
 Sof(H53C)=Sof(H53D)=Sof(C54A)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C56A)=
 Sof(H56C)=Sof(H56D)=Sof(H56E)=Sof(C55A)=Sof(H55C)=Sof(H55D)=1-FVAR(3)
 Sof(H53A)=Sof(H53B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C55)=Sof(H55A)=Sof(H55B)=
 Sof(C54)=Sof(H54D)=Sof(H54E)=FVAR(3)
 Sof(C37A)=Sof(H37A)=Sof(H37B)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C38A)=
 Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(H40E)=1-FVAR(4)
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C37)=Sof(H37C)=Sof(H37D)=Sof(C38)=Sof(H38D)=
 Sof(H38E)=Sof(C39A)=Sof(H39C)=Sof(H39D)=FVAR(4)
        5.a Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C52(H52A,H52B), C51(H51A,H51B), C50(H50A,H50B), C53(H53C,
 H53D), C53(H53A,H53B), C45(H45A,H45B), C45(H45C,H45D), C48(H48A,H48B),
 C44(H44A,H44B), C43(H43D,H43E), C56(H56A,H56B), C47(H47A,H47B), C42(H42A,H42B),
  C37A(H37A,H37B), C46(H46A,H46B), C40(H40A,H40B), C41(H41A,H41B), C55(H55A,
 H55B), C41A(H41C,H41D), C39(H39A,H39B), C37(H37C,H37D), C54(H54D,H54E),
 C46A(H46C,H46D), C47A(H47C,H47D), C48A(H48C,H48D), C38(H38D,H38E), C44A(H44C,
 H44D), C55A(H55C,H55D), C39A(H39C,H39D)
        5.b Me refined with riding coordinates:
 C43(H43A,H43B,H43C)
        5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C30(H30), C26(H26), C36(H36), C32(H32), C4(H4), C5(H5),
 C24(H24), C20(H20), C35(H35), C27(H27), C34(H34), C29(H29), C33(H33), C14(H14),
  C28(H28), C12(H12), C23(H23), C8(H8), C22(H22), C21(H21), C18(H18), C15(H15),
 C9(H9), C16(H16), C11(H11), C10(H10), C17(H17)
        5.d Idealised Me refined as rotating group:
 C54A(H54A,H54B,H54C), C56A(H56C,H56D,H56E), C38A(H38A,H38B,H38C), C42A(H42C,
 H42D,H42E), C40A(H40C,H40D,H40E)
;
_shelx_res_checksum              14904
_shelx_hkl_checksum              96358