Molecularly dispersed nickel complexes on N-doped graphene for electrochemical CO<sub>2</sub> reduction.
Juthathan, Methasit; Chantarojsiri, Teera; Chainok, Kittipong; Butburee, Teera; Thamyongkit, Patchanita; Tuntulani, Thawatchai; Leeladee, Pannee; Dalton transactions (Cambridge, England : 2003) 52 (2023) 11407–11418; doi:10.1039/d3dt00878a

data_7713762
_publ_section_title
;
 Molecularly dispersed nickel complexes on N-doped graphene for
 electrochemical CO<sub>2</sub> reduction.
;
_journal_issue                   33
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11407
_journal_page_last               11418
_journal_paper_doi               10.1039/d3dt00878a
_journal_volume                  52
_journal_year                    2023
_chemical_formula_moiety         'C21 H25 N4 Ni, B F4'
_chemical_formula_sum            'C21 H25 B F4 N4 Ni'
_chemical_formula_weight         478.97
_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             2022-10-26
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-10-26 deposited with the CCDC.	2023-05-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.096(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7951(14)
_cell_length_b                   9.4102(13)
_cell_length_c                   22.736(3)
_cell_measurement_reflns_used    7868
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.557
_cell_measurement_theta_min      2.817
_cell_volume                     2083.8(5)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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_temperature      296(2)
_diffrn_detector                 'Bruker PHOTON 200 area detector'
_diffrn_detector_area_resol_mean 7.39
_diffrn_detector_type            'PHOTON II area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device       'four-circle KAPPA diffractometer'
_diffrn_measurement_device_type  'Bruker D8 QUEST CMOS'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_collimation    '0.5 mm'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0795
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            35456
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.393
_diffrn_reflns_theta_min         2.816
_diffrn_source                   'sealed x-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_type              Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.982
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5719
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0938 before and 0.0765 after correction.
The Ratio of minimum to maximum transmission is 0.7669.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.527
_exptl_crystal_description       block
_exptl_crystal_F_000             992
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.713
_refine_diff_density_min         -0.795
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         5171
_refine_ls_number_restraints     211
_refine_ls_restrained_S_all      1.164
_refine_ls_R_factor_all          0.0855
_refine_ls_R_factor_gt           0.0645
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0429P)^2^+3.9746P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1461
_refine_ls_wR_factor_ref         0.1557
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4058
_reflns_number_total             5171
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00878a2.cif
_cod_data_source_block           2ni_me
_cod_database_code               7713762
_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. Restrained distances
 N4-C21A \\sim N4-C21
 with sigma of 0.02
 N4-C19A \\sim N4-C17 \\sim N4-C18A \\sim N4-C18
 with sigma of 0.02
 C19A-C16 \\sim C17-C16 \\sim C18A-C19 \\sim C19-C18
 with sigma of 0.02
 F1-B1 \\sim F1A-B1A
 with sigma of 0.02
 F4-B1 \\sim F4A-B1A
 with sigma of 0.02
 F3-B1 \\sim F3A-B1A
 with sigma of 0.02
 F4-F2 \\sim F4A-F2A
 with sigma of 0.04
 F1-F2 \\sim F1A-F2A
 with sigma of 0.04
 F3-F4 \\sim F3A-F4A
 with sigma of 0.04
 F3-F1 \\sim F3A-F1A
 with sigma of 0.04
 F3-F2 \\sim F3A-F2A
 with sigma of 0.04
 F2-B1 \\sim F2A-B1A
 with sigma of 0.02
 F4-F1 \\sim F4A-F1A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(F2A) \\sim Ueq, Uanis(F4A) \\sim Ueq, Uanis(B1A) \\sim Ueq, Uanis(F3A)
\\sim Ueq, Uanis(F1A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(B1) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F1) \\sim
Ueq, Uanis(F2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of
0.02
4. Rigid body (RIGU) restrains
 Ni1, N4, C16, C18A, C19, C19A, C21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Ni1, N4, C16, C17, C18, C19, C21
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1A, F2A, F3A, F4A, B1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1, F2, F3, F4, B1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(B1A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(B1)=FVAR(1)
 Fixed Sof: H16A(0.75) H16B(0.75) H16C(0.25) H16D(0.25) C17(0.75) H17A(0.75)
 H17B(0.75) C18(0.75) H18A(0.75) H18B(0.75) C18A(0.25) H18C(0.25) H18D(0.25)
 H19A(0.75) H19B(0.75) H19C(0.25) H19D(0.25) C19A(0.25) H19E(0.25) H19F(0.25)
 C21(0.75) H21A(0.75) H21B(0.75) H21C(0.75) C21A(0.25) H21D(0.25) H21E(0.25)
 H21F(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C16(H16C,H16D), C17(H17A,H17B), C18(H18A,
 H18B), C18A(H18C,H18D), C19(H19A,H19B), C19(H19C,H19D), C19A(H19E,H19F),
 C20(H20A,H20B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C14(H14)
6.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C21A(H21D,H21E,H21F)
;
_shelx_res_checksum              85646
_olex2_submission_special_instructions 'No special instructions were received'