The coordination of alkali-metal nickelates to organic π-systems: synthetic, structural and spectroscopic insights.
Borys, Andryj M.; Vedani, Luca; Hevia, Eva; Dalton transactions (Cambridge, England : 2003) 53 (2024) 8382–8390; doi:10.1039/d4dt00889h

data_7715642
_publ_section_title
;
 The coordination of alkali-metal nickelates to organic &#x3c0;-systems:
 synthetic, structural and spectroscopic insights.
;
_journal_issue                   19
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              8382
_journal_page_last               8390
_journal_paper_doi               10.1039/d4dt00889h
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C50 H76 Li4 N4 Ni2 O2'
_chemical_formula_sum            'C50 H76 Li4 N4 Ni2 O2'
_chemical_formula_weight         910.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-22
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-01-17 deposited with the CCDC.	2024-04-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.7330(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.94240(10)
_cell_length_b                   20.8208(2)
_cell_length_c                   22.7000(2)
_cell_measurement_reflns_used    66293
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      31.9970
_cell_measurement_theta_min      2.3570
_cell_volume                     5145.86(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     10.00  67.00   0.50   10.00    --   13.91-115.00-151.00  114
  2  \w    -67.00  -7.00   0.50   10.00    --  -14.37 115.00 -62.00  120
  3  \w    -94.00 -39.00   0.50   10.00    --  -14.37 174.00  77.00  110
  4  \w    -25.00  50.00   0.50   10.00    --  -14.37  19.00 -90.00  150
  5  \w    -18.00  29.00   0.50   10.00    --  -14.37 -99.00-180.00   94
  6  \w    -83.00 -22.00   0.50   10.00    --  -14.37 140.00 156.49  122
  7  \w    -96.00 -21.00   0.50   10.00    --  -14.37 -38.00  30.00  150
  8  \w    -96.00 -36.00   0.50   10.00    --  -14.37 -38.00 -90.00  120
  9  \w    -25.00  68.00   0.50   10.00    --  -14.37  19.00  60.00  186
 10  \w    -38.00  64.00   0.50   10.00    --  -14.37  57.00  90.00  204
 11  \w    -86.00 -43.50   0.50   10.00    --  -14.37 144.00-107.62   85
 12  \w    -90.00 -42.00   0.50   10.00    --  -14.37-178.00  60.00   96
 13  \w    -80.00 -19.00   0.50   10.00    --  -14.37 135.00  60.81  122
 14  \w    -42.50 -21.00   0.50   10.00    --  -14.37 138.00  79.30   43
 15  \w     47.50  63.00   0.50   10.00    --  -14.37   0.00-150.00   31
 16  \w    -80.00 -45.00   0.50   10.00    --  -14.37 143.00  -2.96   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0636105000
_diffrn_orient_matrix_UB_12      -0.0035148000
_diffrn_orient_matrix_UB_13      0.0090122000
_diffrn_orient_matrix_UB_21      -0.0109358000
_diffrn_orient_matrix_UB_22      0.0068623000
_diffrn_orient_matrix_UB_23      0.0296255000
_diffrn_orient_matrix_UB_31      -0.0089905000
_diffrn_orient_matrix_UB_32      -0.0331815000
_diffrn_orient_matrix_UB_33      0.0051608000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0334
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            154783
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.034
_diffrn_reflns_theta_min         2.052
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.771
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.836
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.175
_exptl_crystal_description       plate
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.123
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.303
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     717
_refine_ls_number_reflns         15039
_refine_ls_number_restraints     245
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0431P)^2^+0.9167P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0764
_refine_ls_wR_factor_ref         0.0809
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12332
_reflns_number_total             15039
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00889h2.cif
_cod_data_source_block           23eh117_amb-1068
_cod_depositor_comments
'Adding full bibliography for 7715639--7715655.cif.'
_cod_database_code               7715642
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C168  H260  Li16  N44  Ni8  O1  '
_shelx_estimated_absorpt_t_max   0.962
_shelx_estimated_absorpt_t_min   0.887
_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. Restrained distances
 C29-C30A \\sim C29A-C30
 with sigma of 0.01
 O2A-C29A \\sim O2-C29
 with sigma of 0.01
 O2A-Li3 \\sim O2-Li3
 with sigma of 0.01
 N4-C49 \\sim N4-C49A
 with sigma of 0.01
 O2A-C31A \\sim O2-C31
 with sigma of 0.01
 C31-C32 \\sim C31A-C32A
 with sigma of 0.01
 N4-C50 \\sim N4-C50A
 with sigma of 0.01
 N4-C48 \\sim N4-C48A
 with sigma of 0.01
 C48A-C47 \\sim C48-C47
 with sigma of 0.01
 O1A-Li2 \\sim O1-Li2
 with sigma of 0.01
 O1A-C25A \\sim O1-C25
 with sigma of 0.01
 O1-C27 \\sim O1A-C27A
 with sigma of 0.01
 C26-C25 \\sim C26A-C25A
 with sigma of 0.01
 C28-C27 \\sim C28A-C27A
 with sigma of 0.01
 N2-C18A \\sim N2-C18
 with sigma of 0.01
 N2-C17A \\sim N2-C17
 with sigma of 0.01
 N2-C16A \\sim N2-C16
 with sigma of 0.01
 C16A-C15 \\sim C16-C15
 with sigma of 0.01
3. Rigid bond restraints
 C30A, C29, O2, C31, C32
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C30, C29A, O2A, C31A, C32A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C28A, C27A, O1A, C25A, C26A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1, C25, C26, C27, C28
 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(C30A) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C29A)
\\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O2A) \\sim Ueq, Uanis(C31) \\sim Ueq,
Uanis(C31A) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C32A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.01
Uanis(C50) \\sim Ueq, Uanis(C50A) \\sim Ueq, Uanis(C49A) \\sim Ueq, Uanis(C49)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C47) \\sim Ueq, Uanis(C48A) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.01
Uanis(C28) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C27A)
\\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(C25) \\sim Ueq,
Uanis(C25A) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C26A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.01
Uanis(C17) \\sim Ueq, Uanis(C17A) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C18A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C15) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C16) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.01
5. Others
 Sof(O2A)=Sof(C30A)=Sof(H30B)=Sof(H30A)=Sof(H30C)=Sof(C29A)=Sof(H29D)=
 Sof(H29C)=Sof(C31A)=Sof(H31C)=Sof(H31D)=Sof(C32A)=Sof(H32D)=Sof(H32E)=
 Sof(H32F)=1-FVAR(1)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C29)=
 Sof(H29B)=Sof(H29A)=Sof(C30)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(O2)=FVAR(1)
 Sof(C49A)=Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C50A)=Sof(H50D)=Sof(H50E)=
 Sof(H50F)=1-FVAR(2)
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 FVAR(2)
 Sof(H47C)=Sof(H47D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=1-FVAR(3)
 Sof(H47A)=Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=FVAR(3)
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C27A)=Sof(H27C)=Sof(H27D)=
 Sof(O1A)=Sof(C25A)=Sof(H25C)=Sof(H25D)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 1-FVAR(4)
 Sof(O1)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C25)=Sof(H25A)=Sof(H25B)=FVAR(4)
 Sof(C18A)=Sof(H18F)=Sof(H18E)=Sof(H18D)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=1-FVAR(5)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 FVAR(5)
 Sof(H15C)=Sof(H15D)=Sof(C16A)=Sof(H16C)=Sof(H16D)=1-FVAR(6)
 Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=FVAR(6)
6.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C15(H15C,H15D), C47(H47A,H47B), C47(H47C,H47D), C16(H16A,
 H16B), C27(H27A,H27B), C48(H48A,H48B), C31(H31A,H31B), C29(H29B,H29A),
 C25(H25A,H25B), C29A(H29D,H29C), C31A(H31C,H31D), C48A(H48C,H48D), C27A(H27C,
 H27D), C25A(H25C,H25D), C16A(H16C,H16D)
6.b Me refined with riding coordinates:
 C26(H26A,H26B,H26C), C49(H49A,H49B,H49C), C18(H18A,H18B,H18C), C17(H17A,H17B,
 H17C), C50(H50A,H50B,H50C), C28(H28A,H28B,H28C), C49A(H49D,H49E,H49F),
 C50A(H50D,H50E,H50F), C28A(H28D,H28E,H28F), C26A(H26D,H26E,H26F), C18A(H18F,
 H18E,H18D), C17A(H17D,H17E,H17F)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C24(H24), C22(H22), C21(H21), C8(H8), C12(H12), C38(H38), C23(H23),
 C34(H34), C11(H11), C10(H10), C44(H44), C40(H40), C9(H9), C3(H3), C6(H6),
 C37(H37), C4(H4), C5(H5), C35(H35), C43(H43), C36(H36), C41(H41), C42(H42)
6.d Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C14(H14A,H14B,H14C), C13(H13A,H13B,
 H13C), C32(H32A,H32B,H32C), C30A(H30B,H30A,H30C), C30(H30D,H30E,H30F),
 C32A(H32D,H32E,H32F)
;
_shelx_res_checksum              3047
_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 1.083
_oxdiff_exptl_absorpt_empirical_full_min 0.934