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_1566779
_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         'C88 H124 Li12 N4 Ni4 O12'
_chemical_formula_sum            'C88 H124 Li12 N4 Ni4 O12'
_chemical_formula_weight         1747.95
_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   geom
_audit_creation_date             2021-10-11
_audit_creation_method
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Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
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_audit_update_record
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2021-12-09 deposited with the CCDC.	2022-04-11 downloaded from the CCDC.
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_cell_angle_alpha                90
_cell_angle_beta                 110.588(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.0297(12)
_cell_length_b                   12.2915(8)
_cell_length_c                   21.1653(13)
_cell_measurement_reflns_used    4988
_cell_measurement_temperature    193.0
_cell_measurement_theta_max      28.14
_cell_measurement_theta_min      2.29
_cell_volume                     4634.5(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        '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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.1732
_diffrn_reflns_av_unetI/netI     0.1243
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            47622
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.250
_diffrn_reflns_theta_min         1.950
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.857
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6948
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1864 before and 0.1036 after correction.
The Ratio of minimum to maximum transmission is 0.9317.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       'rect. Prism'
_exptl_crystal_F_000             1848
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.738
_refine_diff_density_min         -0.810
_refine_diff_density_rms         0.100
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         8389
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.1210
_refine_ls_R_factor_gt           0.0659
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0761P)^2^+2.9155P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1568
_refine_ls_wR_factor_ref         0.2037
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5119
_reflns_number_total             8389
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc01244h5.cif
_cod_data_source_block           jcm04821a_0m_a
_cod_depositor_comments
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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 
;
_cod_database_code               1566779
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.789
_olex2_refinement_description
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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
 C35-C36
 1.54 with sigma of 0.02
3. Rigid bond restraints
 C29, C30, C31, C32
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C37, C38, C39, C40
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C33, C34, C35, C36
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C41, C42, C43, C44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C29 \\sim C30 \\sim C31 \\sim C32: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C37 \\sim C38 \\sim C39 \\sim C40: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C33 \\sim C34 \\sim C35 \\sim C36: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C41 \\sim C42 \\sim C43 \\sim C44: 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:
 C25(H25A,H25B), C27(H27A,H27B), C41(H41A,H41B), C32(H32A,H32B), C33(H33A,
 H33B), C34(H34A,H34B), C40(H40A,H40B), C36(H36A,H36B), C29(H29A,H29B),
 C44(H44A,H44B), C31(H31A,H31B), C38(H38A,H38B), C42(H42A,H42B), C37(H37A,H37B),
  C39(H39A,H39B), C35(H35A,H35B), C43(H43A,H43B), C30(H30A,H30B)
5.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C14(H14), C18(H18), C8(H8), C15(H15), C24(H24), C21(H21), C6(H6),
 C2(H2), C16(H16), C22(H22), C12(H12), C17(H17), C9(H9), C23(H23), C11(H11),
 C4(H4), C10(H10), C5(H5), C3(H3)
5.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C26(H26A,H26B,H26C)
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_shelx_res_checksum              29392
_shelx_hkl_checksum              19681
_olex2_submission_special_instructions 'No special instructions were received'