Electrocatalytic Hydrogen Production by [Ni(7PPh2NH)2]2+: Removing the Distinction Between Endo- and Exo-Protonation Sites
Brown, Houston J. S.; Wiese, Stefan; Roberts, John A. S.; Bullock, R. Morris; Helm, Monte L.; ACS Catalysis 5 (2015) 2116–; doi:10.1021/cs502132y

data_4512816
_publ_section_title
;
 Electrocatalytic Hydrogen Production by [Ni(7PPh2NH)2]2+: Removing the
 Distinction Between Endo- and Exo-Protonation Sites
;
_journal_issue                   4
_journal_name_full               'ACS Catalysis'
_journal_page_first              2116
_journal_paper_doi               10.1021/cs502132y
_journal_volume                  5
_journal_year                    2015
_chemical_formula_moiety
'C34 H39 F3 N2 Ni O2 P4, 2(B F4), 2(C H2 Cl2), C2 H F3 O2'
_chemical_formula_sum            'C38 H44 B2 Cl4 F14 N2 Ni O4 P4'
_chemical_formula_weight         1204.76
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2013.11.15 svn.r2839 for OlexSys, GUI svn.r4713)
;
_cell_angle_alpha                94.9100(10)
_cell_angle_beta                 101.0460(10)
_cell_angle_gamma                109.5540(10)
_cell_formula_units_Z            2
_cell_length_a                   10.3197(2)
_cell_length_b                   13.2465(3)
_cell_length_c                   19.7249(5)
_cell_measurement_reflns_used    9986
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.49
_cell_measurement_theta_min      2.33
_cell_volume                     2460.92(10)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0779
_diffrn_reflns_av_unetI/netI     0.0783
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            53555
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.686
_diffrn_reflns_theta_min         1.653
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.836
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.626
_exptl_crystal_description       block
_exptl_crystal_F_000             1220
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.755
_refine_diff_density_min         -1.822
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     626
_refine_ls_number_reflns         10245
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.1214
_refine_ls_R_factor_gt           0.0725
_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^)+(0.1067P)^2^+8.3208P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1828
_refine_ls_wR_factor_ref         0.2114
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6687
_reflns_number_total             10245
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs502132y_si_002.cif
_cod_data_source_block           helm025_0m
_cod_depositor_comments
'Adding full bibliography for 4512815--4512816.cif.'
_cod_database_code               4512816
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.959
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 N2(H2a,H2b), C1(H1a,H1b), C2(H2c,H2d), C3(H3a,H3b), C4(H4a,H4b), C5(H5a,H5b),
 C6(H6a,H6b), C7(H7a,H7b), C8(H8a,H8b), C1S(H1Sa,H1Sb), C4S(H4Sa,H4Sb)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26),
  C28(H28), C29(H29), C30(H30), C31(H31), C32(H32)
2.c Idealised tetrahedral OH refined as rotating group:
 O2S(H2S)
;
_shelx_res_checksum              41794
_shelx_hkl_checksum              90173