Tuning the overpotential of electrocatalytically active cyclopentadienylnickel complexes containing 1,4-diaza-1,3-butadienes (DAB) for proton reduction.
Sondermann, Christina; Ringenberg, Mark R.; Dalton transactions (Cambridge, England : 2003) 46 (2017) 5143–5146; doi:10.1039/c7dt00960g

data_7042894
_publ_section_title
;
 Tuning the overpotential of electrocatalytically active
 cyclopentadienylnickel complexes containing 1,4-diaza-1,3-butadienes
 (DAB) for proton reduction.
;
_journal_issue                   16
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5143
_journal_page_last               5146
_journal_paper_doi               10.1039/c7dt00960g
_journal_volume                  46
_journal_year                    2017
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C22.99 H19 F5.96 N2 Ni, B F4'
_chemical_formula_sum            'C22.988 H19 B F9.965 N2 Ni'
_chemical_formula_weight         582.12
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_symmetry_Int_Tables_number      29
_symmetry_space_group_name_Hall  'P 2c -2ac'
_symmetry_space_group_name_H-M   'P c a 21'
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-01-21
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2016-09-14 deposited with the CCDC.
2017-03-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.7420(17)
_cell_length_b                   7.5757(5)
_cell_length_c                   15.8268(13)
_cell_measurement_reflns_used    3450
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.390
_cell_measurement_theta_min      2.335
_cell_volume                     2367.0(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      99.99
_diffrn_measured_fraction_theta_full 0.9765
_diffrn_measured_fraction_theta_max 0.9765
_diffrn_measurement_device_type  'APEXII, Bruker-AXS'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0703
_diffrn_reflns_av_unetI/netI     0.0946
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            16211
_diffrn_reflns_theta_full        26.3876
_diffrn_reflns_theta_max         26.39
_diffrn_reflns_theta_min         2.06
_exptl_absorpt_coefficient_mu    0.913
_exptl_absorpt_correction_T_max  0.8945
_exptl_absorpt_correction_T_min  0.7908
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   '(de Meulenaar et al., 1965)'
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.6333
_exptl_crystal_description       prism
_exptl_crystal_F_000             1176.7839
_exptl_crystal_recrystallization_method 'slow evaporation of CH2Cl2'
_exptl_crystal_size_max          0.209
_exptl_crystal_size_mid          0.188
_exptl_crystal_size_min          0.116
_refine_diff_density_max         0.7571
_refine_diff_density_min         -0.6971
_refine_diff_density_rms         0.1439
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   -0.00(2)
_refine_ls_d_res_high            0.7996
_refine_ls_d_res_low             9.8710
_refine_ls_goodness_of_fit_ref   1.0121
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    35
_refine_ls_number_parameters     336
_refine_ls_number_reflns         4737
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.0097
_refine_ls_R_factor_all          0.0835
_refine_ls_R_factor_gt           0.0473
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0309P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0772
_refine_ls_wR_factor_ref         0.0885
_reflns_Friedel_coverage         0.952
_reflns_limit_h_max              24
_reflns_limit_h_min              -24
_reflns_limit_k_max              9
_reflns_limit_k_min              -9
_reflns_limit_l_max              17
_reflns_limit_l_min              -19
_reflns_number_gt                3450
_reflns_number_total             4737
_reflns_threshold_expression     I>=2u(I)
_iucr_refine_instructions_details
'The proposed model includes two trifluromethyl groups. Similar, pseudo-threefold geometry was imposed on the disordered trifluromethyl groups using effective standard deviations of 0.01 and 0.02\%A for bond lengths and angles, respectively.'
_cod_data_source_file            c7dt00960g2.cif
_cod_data_source_block           ac352
_cod_original_sg_symbol_Hall     ' P 2c -2ac'
_cod_database_code               7042894
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C23-C22 \\sim C23-F6 \\sim C23-F5 \\sim C23-F4
 with sigma of 0.02
 F4-F6 \\sim F6-F5 \\sim F4-F5
 with sigma of 0.02
 C23-C22 \\sim C23-F6 \\sim C23-F5 \\sim C23-F4
 with sigma of 0.02
 F4-F6 \\sim F6-F5 \\sim F4-F5
 with sigma of 0.02
 C23-C22 \\sim C23-F6 \\sim C23-F5 \\sim C23-F4
 with sigma of 0.02
 F4-F6 \\sim F6-F5 \\sim F4-F5
 with sigma of 0.02
3. Others
 Sof(C23)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13),
 C14(H14), C18(H18), C19(H19), C20(H20), C21(H21)
4.b Idealised Me refined as rotating group:
 C8(H8a,H8b,H8c), C9(H9a,H9b,H9c)
;
_olex2_exptl_crystal_mounting_method
'crystals were mounted using perfluoropolyalkylether from ABCR viscosity 1800 cts on to a cryoloop'
_olex2_submission_special_instructions 'No special instructions were received'