#------------------------------------------------------------------------------
#$Date: 2025-08-20 17:59:05 +0300 (Wed, 20 Aug 2025) $
#$Revision: 301833 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/11/96/4119610.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4119610
loop_
_publ_author_name
'Michael P. Stewart'
'Ming-Hsun Ho'
'Stefan Wiese'
'Mary Lou Lindstrom'
'Colleen E. Thogerson'
'Simone Raugei'
'R. Morris Bullock'
'Monte L. Helm'
_publ_section_title
;
 High Catalytic Rates for Hydrogen Production Using Nickel
 Electrocatalysts with Seven-Membered Cyclic Diphosphine Ligands
 Containing One Pendant Amine
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6033
_journal_page_last               6046
_journal_paper_doi               10.1021/ja400181a
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C44 H44 Br2 N2 Ni P4, 2(B F4), 2(C2 H3 N)'
_chemical_formula_sum            'C48 H50 B2 Br2 F8 N4 Ni P4'
_chemical_formula_weight         1198.95
_chemical_name_common            '[Ni(7PPh2NPhBr1)2](BF4)2'
_space_group_IT_number           2
_symmetry_cell_setting           triclinic
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                91.3400(10)
_cell_angle_beta                 98.6610(10)
_cell_angle_gamma                103.3590(10)
_cell_formula_units_Z            1
_cell_length_a                   10.0496(6)
_cell_length_b                   10.1294(6)
_cell_length_c                   12.2373(7)
_cell_measurement_reflns_used    9853
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      31.66
_cell_measurement_theta_min      2.48
_cell_volume                     1195.99(12)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_sigmaI/netI    0.0226
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            19929
_diffrn_reflns_theta_full        27.10
_diffrn_reflns_theta_max         27.10
_diffrn_reflns_theta_min         1.69
_exptl_absorpt_coefficient_mu    2.282
_exptl_absorpt_correction_T_max  0.8752
_exptl_absorpt_correction_T_min  0.7406
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS; (Sheldrick, 2006)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.665
_exptl_crystal_description       block
_exptl_crystal_F_000             606
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.790
_refine_diff_density_min         -0.801
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     314
_refine_ls_number_reflns         5218
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0422
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0563P)²+4.1570P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1177
_refine_ls_wR_factor_ref         0.1208
_reflns_number_gt                4743
_reflns_number_total             5218
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja400181a_si_002_3.cif
_cod_data_source_block           helm006_0m
_cod_original_sg_symbol_Hall     -P1
_cod_database_code               4119610
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
Ni1 Ni 0.5000 0.5000 0.5000 0.01034(13) Uani 1 2 d S
Br1 Br 0.86410(4) 0.11076(4) 0.36134(3) 0.02371(12) Uani 1 1 d .
P2 P 0.43890(8) 0.45865(8) 0.66393(6) 0.01076(16) Uani 1 1 d .
P1 P 0.27635(8) 0.39581(8) 0.44957(6) 0.01066(16) Uani 1 1 d .
N1 N 0.3703(3) 0.1957(3) 0.5669(2) 0.0132(5) Uani 1 1 d .
C4 C 0.3914(3) 0.2682(3) 0.6736(3) 0.0136(6) Uani 1 1 d .
H4A H 0.4662 0.2408 0.7234 0.016 Uiso 1 1 calc R
H4B H 0.3056 0.2425 0.7065 0.016 Uiso 1 1 calc R
C3 C 0.2493(3) 0.2155(3) 0.4950(3) 0.0134(6) Uani 1 1 d .
H3A H 0.1686 0.1952 0.5345 0.016 Uiso 1 1 calc R
H3B H 0.2288 0.1515 0.4289 0.016 Uiso 1 1 calc R
C2 C 0.1831(3) 0.4706(3) 0.5430(3) 0.0150(6) Uani 1 1 d .
H2A H 0.1597 0.5532 0.5117 0.018 Uiso 1 1 calc R
H2B H 0.0956 0.4049 0.5501 0.018 Uiso 1 1 calc R
C1 C 0.2729(3) 0.5080(3) 0.6583(3) 0.0147(6) Uani 1 1 d .
H1A H 0.2220 0.4613 0.7151 0.018 Uiso 1 1 calc R
H1B H 0.2909 0.6072 0.6751 0.018 Uiso 1 1 calc R
C17 C 0.5355(3) 0.5253(3) 0.7984(3) 0.0138(6) Uani 1 1 d .
C22 C 0.6265(3) 0.4566(3) 0.8565(3) 0.0173(6) Uani 1 1 d .
H22 H 0.6417 0.3764 0.8240 0.021 Uiso 1 1 calc R
C21 C 0.6949(4) 0.5056(4) 0.9622(3) 0.0213(7) Uani 1 1 d .
H21 H 0.7568 0.4586 1.0016 0.026 Uiso 1 1 calc R
C20 C 0.6734(4) 0.6222(4) 1.0103(3) 0.0228(7) Uani 1 1 d .
H20 H 0.7200 0.6547 1.0827 0.027 Uiso 1 1 calc R
C19 C 0.5841(4) 0.6916(4) 0.9532(3) 0.0226(7) Uani 1 1 d .
H19 H 0.5696 0.7718 0.9864 0.027 Uiso 1 1 calc R
C18 C 0.5155(4) 0.6444(4) 0.8475(3) 0.0188(7) Uani 1 1 d .
H18 H 0.4550 0.6928 0.8082 0.023 Uiso 1 1 calc R
C11 C 0.1717(3) 0.3829(3) 0.3139(3) 0.0123(6) Uani 1 1 d .
C12 C 0.1635(3) 0.2726(3) 0.2394(3) 0.0152(6) Uani 1 1 d .
H12 H 0.2158 0.2074 0.2594 0.018 Uiso 1 1 calc R
C13 C 0.0801(3) 0.2585(3) 0.1374(3) 0.0176(6) Uani 1 1 d .
H13 H 0.0737 0.1826 0.0880 0.021 Uiso 1 1 calc R
C14 C 0.0050(3) 0.3550(4) 0.1065(3) 0.0176(6) Uani 1 1 d .
H14 H -0.0519 0.3451 0.0360 0.021 Uiso 1 1 calc R
C15 C 0.0132(3) 0.4655(3) 0.1784(3) 0.0172(6) Uani 1 1 d .
H15 H -0.0379 0.5313 0.1570 0.021 Uiso 1 1 calc R
C16 C 0.0965(3) 0.4801(3) 0.2822(3) 0.0154(6) Uani 1 1 d .
H16 H 0.1023 0.5559 0.3313 0.018 Uiso 1 1 calc R
C5 C 0.4872(3) 0.1853(3) 0.5184(3) 0.0128(6) Uani 1 1 d .
C10 C 0.4699(3) 0.1353(3) 0.4082(3) 0.0159(6) Uani 1 1 d .
H10 H 0.3803 0.1156 0.3646 0.019 Uiso 1 1 calc R
C9 C 0.5815(4) 0.1141(3) 0.3616(3) 0.0167(6) Uani 1 1 d .
H9 H 0.5681 0.0799 0.2868 0.020 Uiso 1 1 calc R
C8 C 0.7128(3) 0.1431(3) 0.4248(3) 0.0163(6) Uani 1 1 d .
C7 C 0.7326(3) 0.1917(3) 0.5338(3) 0.0179(7) Uani 1 1 d .
H7 H 0.8224 0.2098 0.5769 0.021 Uiso 1 1 calc R
C6 C 0.6211(3) 0.2143(3) 0.5805(3) 0.0166(6) Uani 1 1 d .
H6 H 0.6358 0.2497 0.6551 0.020 Uiso 1 1 calc R
B1 B 0.0316(4) 0.8481(4) 0.2215(3) 0.0207(8) Uani 1 1 d .
F4 F 0.0990(3) 0.9661(2) 0.2847(2) 0.0316(5) Uani 1 1 d .
F3 F -0.0516(3) 0.7608(2) 0.2854(2) 0.0340(6) Uani 1 1 d .
F1 F 0.1289(3) 0.7824(2) 0.1905(2) 0.0346(6) Uani 1 1 d .
F2 F -0.0488(3) 0.8785(3) 0.1282(2) 0.0464(7) Uani 1 1 d .
N1S N 0.5492(4) 0.0924(4) 0.8769(3) 0.0313(8) Uani 1 1 d .
C2S C 0.6386(4) 0.0725(4) 0.9361(3) 0.0248(8) Uani 1 1 d .
C1S C 0.7564(5) 0.0480(5) 1.0134(4) 0.0413(11) Uani 1 1 d .
H1S1 H 0.8402 0.0695 0.9789 0.062 Uiso 1 1 calc R
H1S2 H 0.7369 -0.0477 1.0312 0.062 Uiso 1 1 calc R
H1S3 H 0.7705 0.1058 1.0814 0.062 Uiso 1 1 calc R
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
P2 Ni1 P2 179.999(1) . 2_666
P2 Ni1 P1 100.30(3) . 2_666
P2 Ni1 P1 79.70(3) 2_666 2_666
P2 Ni1 P1 79.70(3) . .
P2 Ni1 P1 100.30(3) 2_666 .
P1 Ni1 P1 180.0 2_666 .
C17 P2 C1 104.66(15) . .
C17 P2 C4 105.12(14) . .
C1 P2 C4 104.07(15) . .
C17 P2 Ni1 127.97(11) . .
C1 P2 Ni1 105.11(11) . .
C4 P2 Ni1 107.67(10) . .
C11 P1 C2 105.29(14) . .
C11 P1 C3 105.21(14) . .
C2 P1 C3 101.24(15) . .
C11 P1 Ni1 128.11(10) . .
C2 P1 Ni1 105.60(11) . .
C3 P1 Ni1 108.32(10) . .
C5 N1 C3 118.1(3) . .
C5 N1 C4 119.1(3) . .
C3 N1 C4 112.1(3) . .
N1 C4 P2 112.4(2) . .
N1 C4 H4A 109.1 . .
P2 C4 H4A 109.1 . .
N1 C4 H4B 109.1 . .
P2 C4 H4B 109.1 . .
H4A C4 H4B 107.9 . .
N1 C3 P1 111.4(2) . .
N1 C3 H3A 109.3 . .
P1 C3 H3A 109.3 . .
N1 C3 H3B 109.3 . .
P1 C3 H3B 109.3 . .
H3A C3 H3B 108.0 . .
C1 C2 P1 110.4(2) . .
C1 C2 H2A 109.6 . .
P1 C2 H2A 109.6 . .
C1 C2 H2B 109.6 . .
P1 C2 H2B 109.6 . .
H2A C2 H2B 108.1 . .
C2 C1 P2 111.1(2) . .
C2 C1 H1A 109.4 . .
P2 C1 H1A 109.4 . .
C2 C1 H1B 109.4 . .
P2 C1 H1B 109.4 . .
H1A C1 H1B 108.0 . .
C22 C17 C18 119.2(3) . .
C22 C17 P2 120.6(3) . .
C18 C17 P2 120.1(3) . .
C21 C22 C17 119.9(3) . .
C21 C22 H22 120.0 . .
C17 C22 H22 120.0 . .
C20 C21 C22 120.4(3) . .
C20 C21 H21 119.8 . .
C22 C21 H21 119.8 . .
C21 C20 C19 120.1(3) . .
C21 C20 H20 120.0 . .
C19 C20 H20 120.0 . .
C20 C19 C18 120.2(3) . .
C20 C19 H19 119.9 . .
C18 C19 H19 119.9 . .
C19 C18 C17 120.1(3) . .
C19 C18 H18 119.9 . .
C17 C18 H18 119.9 . .
C16 C11 C12 119.1(3) . .
C16 C11 P1 121.2(2) . .
C12 C11 P1 119.7(2) . .
C13 C12 C11 120.4(3) . .
C13 C12 H12 119.8 . .
C11 C12 H12 119.8 . .
C12 C13 C14 120.2(3) . .
C12 C13 H13 119.9 . .
C14 C13 H13 119.9 . .
C15 C14 C13 120.2(3) . .
C15 C14 H14 119.9 . .
C13 C14 H14 119.9 . .
C14 C15 C16 120.0(3) . .
C14 C15 H15 120.0 . .
C16 C15 H15 120.0 . .
C15 C16 C11 120.0(3) . .
C15 C16 H16 120.0 . .
C11 C16 H16 120.0 . .
C10 C5 C6 118.2(3) . .
C10 C5 N1 120.1(3) . .
C6 C5 N1 121.6(3) . .
C9 C10 C5 121.1(3) . .
C9 C10 H10 119.5 . .
C5 C10 H10 119.5 . .
C10 C9 C8 119.8(3) . .
C10 C9 H9 120.1 . .
C8 C9 H9 120.1 . .
C7 C8 C9 120.3(3) . .
C7 C8 Br1 120.2(3) . .
C9 C8 Br1 119.5(3) . .
C8 C7 C6 120.1(3) . .
C8 C7 H7 120.0 . .
C6 C7 H7 120.0 . .
C7 C6 C5 120.6(3) . .
C7 C6 H6 119.7 . .
C5 C6 H6 119.7 . .
F2 B1 F4 109.9(3) . .
F2 B1 F1 109.7(3) . .
F4 B1 F1 109.5(3) . .
F2 B1 F3 110.3(3) . .
F4 B1 F3 109.1(3) . .
F1 B1 F3 108.2(3) . .
N1S C2S C1S 179.4(4) . .
C2S C1S H1S1 109.5 . .
C2S C1S H1S2 109.5 . .
H1S1 C1S H1S2 109.5 . .
C2S C1S H1S3 109.5 . .
H1S1 C1S H1S3 109.5 . .
H1S2 C1S H1S3 109.5 . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Ni1 P2 2.2064(8) .
Ni1 P2 2.2064(8) 2_666
Ni1 P1 2.2365(8) 2_666
Ni1 P1 2.2365(8) .
Br1 C8 1.896(3) .
P2 C17 1.809(3) .
P2 C1 1.841(3) .
P2 C4 1.888(3) .
P1 C11 1.811(3) .
P1 C2 1.836(3) .
P1 C3 1.893(3) .
N1 C5 1.417(4) .
N1 C3 1.446(4) .
N1 C4 1.446(4) .
C4 H4A 0.9900 .
C4 H4B 0.9900 .
C3 H3A 0.9900 .
C3 H3B 0.9900 .
C2 C1 1.543(4) .
C2 H2A 0.9900 .
C2 H2B 0.9900 .
C1 H1A 0.9900 .
C1 H1B 0.9900 .
C17 C22 1.395(5) .
C17 C18 1.404(5) .
C22 C21 1.391(5) .
C22 H22 0.9500 .
C21 C20 1.383(6) .
C21 H21 0.9500 .
C20 C19 1.383(6) .
C20 H20 0.9500 .
C19 C18 1.388(5) .
C19 H19 0.9500 .
C18 H18 0.9500 .
C11 C16 1.401(4) .
C11 C12 1.405(4) .
C12 C13 1.380(5) .
C12 H12 0.9500 .
C13 C14 1.393(5) .
C13 H13 0.9500 .
C14 C15 1.387(5) .
C14 H14 0.9500 .
C15 C16 1.397(4) .
C15 H15 0.9500 .
C16 H16 0.9500 .
C5 C10 1.401(5) .
C5 C6 1.405(4) .
C10 C9 1.388(5) .
C10 H10 0.9500 .
C9 C8 1.389(5) .
C9 H9 0.9500 .
C8 C7 1.380(5) .
C7 C6 1.393(5) .
C7 H7 0.9500 .
C6 H6 0.9500 .
B1 F2 1.380(5) .
B1 F4 1.383(5) .
B1 F1 1.395(5) .
B1 F3 1.407(5) .
N1S C2S 1.126(5) .
C2S C1S 1.472(6) .
C1S H1S1 0.9800 .
C1S H1S2 0.9800 .
C1S H1S3 0.9800 .
loop_
_cod_related_entry_id
_cod_related_entry_database
_cod_related_entry_code
1 PubChem 168333248
