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_1566777
_publ_section_title
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 Unmasking the constitution and bonding of the proposed lithium nickelate
 &#x201C;Li3NiPh3(solv)3&#x201D;: Revealing the hidden C6H4 ligand
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_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC01244H
_journal_year                    2022
_chemical_formula_moiety         'C64 H112 Br2 Li6 Ni2 O8'
_chemical_formula_sum            'C64 H112 Br2 Li6 Ni2 O8'
_chemical_formula_weight         1328.41
_chemical_melting_point          ?
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2021-07-26
_audit_creation_method
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Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-12-09 deposited with the CCDC.	2022-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.001(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.6770(8)
_cell_length_b                   19.8681(7)
_cell_length_c                   39.5750(16)
_cell_measurement_reflns_used    9884
_cell_measurement_temperature    193.0
_cell_measurement_theta_max      25.52
_cell_measurement_theta_min      2.29
_cell_volume                     14683.1(10)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      193.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0491
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            148527
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.123
_diffrn_reflns_theta_min         2.050
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.646
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.5715
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0924 before and 0.0475 after correction.
The Ratio of minimum to maximum transmission is 0.7668.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.202
_exptl_crystal_description       block
_exptl_crystal_F_000             5632
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.977
_refine_diff_density_min         -1.210
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1533
_refine_ls_number_reflns         32337
_refine_ls_number_restraints     98
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.1060
_refine_ls_R_factor_gt           0.0675
_refine_ls_shift/su_max          0.016
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0837P)^2^+36.1842P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1755
_refine_ls_wR_factor_ref         0.1962
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21445
_reflns_number_total             32337
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01244h5.cif
_cod_data_source_block           jcm00321a_0m_a
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C128 H224 Br4 Li12 Ni4 O16'
_cod_original_formula_weight         2656.82
_cod_original_formula_moiety         '2(C64 H112 Br2 Li6 Ni2 O8)'
_cod_original_formula_units_Z            4
_cod_database_code               1566777
_shelx_shelxl_version_number     2014/7
_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
 C63-C64
 1.5 with sigma of 0.02
 C109-C110
 1.5 with sigma of 0.02
 C61-C63
 3 with sigma of 0.02
 C111-C112
 1.5 with sigma of 0.02
 C121-C122
 1.5 with sigma of 0.02
3. Rigid bond restraints
 C62, C61
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C63, C64
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C128, C127, O16, C125, C126
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C38, C37, O3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O9, C107, C108
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C62 \\sim C61: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C63 \\sim C64: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
O12 \\sim C112 \\sim C111: within 2A with sigma of 0.00001 and sigma for
terminal atoms of 0.00002 within 2A
C110 \\sim C109: within 2A with sigma of 0.00001 and sigma for terminal atoms
of 0.00002 within 2A
C128 \\sim C127 \\sim O16 \\sim C125 \\sim C126: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C38 \\sim C37 \\sim O3: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
O9 \\sim C107 \\sim C108: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
5.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C79(H79A,H79B), C83(H83A,H83B), C80(H80A,H80B), C84(H84A,
 H84B), C16(H16A,H16B), C19(H19A,H19B), C20(H20A,H20B), C55(H55A,H55B),
 C113(H11A,H11B), C33(H33A,H33B), C97(H97A,H97B), C51(H51A,H51B), C115(H11C,
 H11D), C99(H99A,H99B), C41(H41A,H41B), C39(H39A,H39B), C105(H10A,H10B),
 C35(H35A,H35B), C53(H53A,H53B), C45(H45A,H45B), C117(H11H,H11I), C57(H57A,
 H57B), C123(H12A,H12B), C103(H10F,H10G), C119(H11J,H11K), C43(H43A,H43B),
 C47(H47A,H47B), C121(H12C,H12D), C49(H49A,H49B), C107(H10K,H10L), C101(H10M,
 H10N), C59(H59A,H59B), C125(H12K,H12L), C127(H12S,H12T), C61(H61A,H61B),
 C37(H37A,H37B), C63(H63A,H63B), C109(H10X,H10Y), C112(H11X,H11Y)
5.b Aromatic/amide H refined with riding coordinates:
 C90(H90), C70(H70), C12(H12), C6(H6), C87(H87), C86(H86), C72(H72), C66(H66),
 C26(H26), C96(H96), C89(H89), C73(H73), C32(H32), C76(H76), C8(H8), C2(H2),
 C11(H11), C69(H69), C22(H22), C5(H5), C92(H92), C88(H88), C10(H10), C25(H25),
 C4(H4), C28(H28), C31(H31), C3(H3), C67(H67), C75(H75), C24(H24), C23(H23),
 C68(H68), C74(H74), C30(H30), C93(H93), C9(H9), C29(H29), C95(H95), C94(H94)
5.c Idealised Me refined as rotating group:
 C58(H58A,H58B,H58C), C56(H56A,H56B,H56C), C114(H11E,H11F,H11G), C52(H52A,H52B,
 H52C), C42(H42A,H42B,H42C), C106(H10C,H10D,H10E), C34(H34A,H34B,H34C),
 C102(H10H,H10I,H10J), C36(H36A,H36B,H36C), C98(H98A,H98B,H98C), C44(H44A,H44B,
 H44C), C124(H12E,H12F,H12G), C54(H54A,H54B,H54C), C60(H60A,H60B,H60C),
 C62(H62A,H62B,H62C), C120(H12H,H12I,H12J), C48(H48A,H48B,H48C), C116(H11L,H11M,
 H11N), C118(H11O,H11P,H11Q), C104(H10O,H10P,H10Q), C122(H12M,H12N,H12O),
 C100(H10R,H10S,H10T), C46(H46A,H46B,H46C), C64(H64A,H64B,H64C), C128(H12P,H12Q,
 H12R), C50(H50A,H50B,H50C), C40(H40A,H40B,H40C), C108(H10U,H10V,H10W),
 C38(H38A,H38B,H38C), C110(H11R,H11S,H11T), C111(H11U,H11V,H11W), C126(H12U,
 H12V,H12W)
;
_shelx_res_checksum              79718
_shelx_hkl_checksum              16095
_olex2_submission_special_instructions 'No special instructions were received'