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#$Date: 2025-08-20 17:59:05 +0300 (Wed, 20 Aug 2025) $
#$Revision: 301833 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/11/96/4119609.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_4119609
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         'C46 H50 N2 Ni P4, 2(B F4), 2(C2 H3 N)'
_chemical_formula_sum            'C50 H56 B2 F8 N4 Ni P4'
_chemical_formula_weight         1069.20
_chemical_name_common            '[Ni(7PPh2NPhMe)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                93.072(2)
_cell_angle_beta                 93.8470(10)
_cell_angle_gamma                104.0340(10)
_cell_formula_units_Z            1
_cell_length_a                   9.5270(3)
_cell_length_b                   10.7718(3)
_cell_length_c                   12.1475(3)
_cell_measurement_reflns_used    9916
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      28.86
_cell_measurement_theta_min      2.49
_cell_volume                     1203.53(6)
_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      173(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0356
_diffrn_reflns_av_sigmaI/netI    0.0353
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            24620
_diffrn_reflns_theta_full        28.28
_diffrn_reflns_theta_max         28.28
_diffrn_reflns_theta_min         2.21
_exptl_absorpt_coefficient_mu    0.609
_exptl_absorpt_correction_T_max  0.9473
_exptl_absorpt_correction_T_min  0.8778
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS; (Sheldrick, 2006)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.475
_exptl_crystal_description       block
_exptl_crystal_F_000             554
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.701
_refine_diff_density_min         -0.458
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     315
_refine_ls_number_reflns         5972
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0516
_refine_ls_R_factor_gt           0.0377
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.0461P)²+0.7542P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0909
_refine_ls_wR_factor_ref         0.0979
_reflns_number_gt                4821
_reflns_number_total             5972
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja400181a_si_002_2.cif
_cod_data_source_block           helm082_0m
_cod_original_sg_symbol_Hall     -P1
_cod_database_code               4119609
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 0.0000 0.01473(9) Uani 1 2 d S
P1 P 0.43545(5) 0.50255(5) 0.17080(4) 0.01653(11) Uani 1 1 d .
P2 P 0.73729(5) 0.52603(4) 0.03355(4) 0.01631(11) Uani 1 1 d .
N1 N 0.33631(17) 0.70685(15) 0.09244(13) 0.0202(3) Uani 1 1 d .
C1 C 0.3618(2) 0.64788(19) 0.19362(16) 0.0229(4) Uani 1 1 d .
H1A H 0.2695 0.6227 0.2290 0.027 Uiso 1 1 calc R
H1B H 0.4313 0.7117 0.2451 0.027 Uiso 1 1 calc R
C2 C 0.2196(2) 0.62692(19) 0.01986(17) 0.0221(4) Uani 1 1 d .
H2A H 0.1991 0.6756 -0.0436 0.027 Uiso 1 1 calc R
H2B H 0.1310 0.6053 0.0602 0.027 Uiso 1 1 calc R
C3 C 0.8218(2) 0.6416(2) -0.06280(16) 0.0246(4) Uani 1 1 d .
H3A H 0.8399 0.7297 -0.0275 0.030 Uiso 1 1 calc R
H3B H 0.9165 0.6259 -0.0797 0.030 Uiso 1 1 calc R
C4 C 0.2746(2) 0.36900(19) 0.17021(16) 0.0238(4) Uani 1 1 d .
H4A H 0.3049 0.2880 0.1781 0.029 Uiso 1 1 calc R
H4B H 0.2190 0.3825 0.2339 0.029 Uiso 1 1 calc R
C5 C 0.5431(2) 0.49166(19) 0.29668(15) 0.0202(4) Uani 1 1 d .
C6 C 0.6193(2) 0.6012(2) 0.36106(17) 0.0256(4) Uani 1 1 d .
H6 H 0.6203 0.6838 0.3368 0.031 Uiso 1 1 calc R
C7 C 0.6938(2) 0.5898(2) 0.46067(18) 0.0318(5) Uani 1 1 d .
H7 H 0.7457 0.6645 0.5046 0.038 Uiso 1 1 calc R
C8 C 0.6923(2) 0.4700(2) 0.49591(17) 0.0318(5) Uani 1 1 d .
H8 H 0.7407 0.4626 0.5653 0.038 Uiso 1 1 calc R
C9 C 0.6214(2) 0.3610(2) 0.43133(18) 0.0311(5) Uani 1 1 d .
H9 H 0.6235 0.2788 0.4552 0.037 Uiso 1 1 calc R
C10 C 0.5467(2) 0.3712(2) 0.33122(17) 0.0260(4) Uani 1 1 d .
H10 H 0.4983 0.2961 0.2864 0.031 Uiso 1 1 calc R
C11 C 0.4573(2) 0.77943(18) 0.04383(16) 0.0207(4) Uani 1 1 d .
C12 C 0.4451(2) 0.8156(2) -0.06468(17) 0.0286(5) Uani 1 1 d .
H12 H 0.3563 0.7839 -0.1091 0.034 Uiso 1 1 calc R
C13 C 0.5607(3) 0.8971(2) -0.10824(19) 0.0328(5) Uani 1 1 d .
H13 H 0.5487 0.9209 -0.1818 0.039 Uiso 1 1 calc R
C14 C 0.6933(2) 0.9449(2) -0.0474(2) 0.0325(5) Uani 1 1 d .
C15 C 0.7045(2) 0.9101(2) 0.0599(2) 0.0365(6) Uani 1 1 d .
H15 H 0.7933 0.9431 0.1041 0.044 Uiso 1 1 calc R
C16 C 0.5906(2) 0.8286(2) 0.1054(2) 0.0313(5) Uani 1 1 d .
H16 H 0.6033 0.8060 0.1793 0.038 Uiso 1 1 calc R
C17 C 0.8197(3) 1.0323(2) -0.0954(3) 0.0479(7) Uani 1 1 d .
H17A H 0.8757 0.9805 -0.1335 0.072 Uiso 1 1 calc R
H17B H 0.8821 1.0879 -0.0357 0.072 Uiso 1 1 calc R
H17C H 0.7833 1.0852 -0.1481 0.072 Uiso 1 1 calc R
C18 C 0.84871(19) 0.57437(18) 0.16292(15) 0.0180(4) Uani 1 1 d .
C19 C 0.9042(2) 0.70401(19) 0.19513(17) 0.0235(4) Uani 1 1 d .
H19 H 0.8829 0.7669 0.1493 0.028 Uiso 1 1 calc R
C20 C 0.9904(2) 0.7420(2) 0.29354(18) 0.0280(4) Uani 1 1 d .
H20 H 1.0273 0.8308 0.3149 0.034 Uiso 1 1 calc R
C21 C 1.0226(2) 0.6519(2) 0.36052(17) 0.0268(4) Uani 1 1 d .
H21 H 1.0822 0.6783 0.4276 0.032 Uiso 1 1 calc R
C22 C 0.9679(2) 0.5224(2) 0.32967(16) 0.0243(4) Uani 1 1 d .
H22 H 0.9903 0.4602 0.3758 0.029 Uiso 1 1 calc R
C23 C 0.8807(2) 0.48321(18) 0.23205(16) 0.0205(4) Uani 1 1 d .
H23 H 0.8425 0.3943 0.2120 0.025 Uiso 1 1 calc R
B1 B 0.9317(3) 0.1559(3) 0.2926(2) 0.0367(6) Uani 1 1 d .
F1 F 0.9278(2) 0.02801(14) 0.29559(14) 0.0548(4) Uani 1 1 d .
F2 F 0.8148(3) 0.1812(2) 0.3375(2) 0.1097(10) Uani 1 1 d .
F3 F 0.92984(18) 0.19076(14) 0.18433(13) 0.0521(4) Uani 1 1 d .
F4 F 1.0557(3) 0.2292(2) 0.34972(17) 0.0906(8) Uani 1 1 d .
N1S N 0.5969(4) 1.1053(3) 0.6256(2) 0.0728(8) Uani 1 1 d .
C1S C 0.6591(3) 1.0396(3) 0.5831(2) 0.0501(7) Uani 1 1 d .
C2S C 0.7366(4) 0.9584(3) 0.5276(3) 0.0636(8) Uani 1 1 d .
H2S1 H 0.8136 1.0112 0.4886 0.095 Uiso 1 1 calc R
H2S2 H 0.6691 0.8971 0.4743 0.095 Uiso 1 1 calc R
H2S3 H 0.7795 0.9116 0.5821 0.095 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'
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
P1 Ni1 P1 180.0 . 2_665
P1 Ni1 P2 99.899(17) . .
P1 Ni1 P2 80.102(17) 2_665 .
P1 Ni1 P2 80.101(17) . 2_665
P1 Ni1 P2 99.898(17) 2_665 2_665
P2 Ni1 P2 180.0 . 2_665
C5 P1 C4 104.42(9) . .
C5 P1 C1 106.44(9) . .
C4 P1 C1 103.31(9) . .
C5 P1 Ni1 127.85(6) . .
C4 P1 Ni1 105.20(7) . .
C1 P1 Ni1 107.17(6) . .
C18 P2 C3 104.49(9) . .
C18 P2 C2 105.43(9) . 2_665
C3 P2 C2 102.63(10) . 2_665
C18 P2 Ni1 128.95(6) . .
C3 P2 Ni1 105.71(7) . .
C2 P2 Ni1 106.84(6) 2_665 .
C11 N1 C2 117.80(16) . .
C11 N1 C1 118.30(16) . .
C2 N1 C1 112.41(16) . .
N1 C1 P1 113.06(13) . .
N1 C1 H1A 109.0 . .
P1 C1 H1A 109.0 . .
N1 C1 H1B 109.0 . .
P1 C1 H1B 109.0 . .
H1A C1 H1B 107.8 . .
N1 C2 P2 112.58(13) . 2_665
N1 C2 H2A 109.1 . .
P2 C2 H2A 109.1 2_665 .
N1 C2 H2B 109.1 . .
P2 C2 H2B 109.1 2_665 .
H2A C2 H2B 107.8 . .
C4 C3 P2 111.42(13) 2_665 .
C4 C3 H3A 109.3 2_665 .
P2 C3 H3A 109.3 . .
C4 C3 H3B 109.3 2_665 .
P2 C3 H3B 109.3 . .
H3A C3 H3B 108.0 . .
C3 C4 P1 110.61(13) 2_665 .
C3 C4 H4A 109.5 2_665 .
P1 C4 H4A 109.5 . .
C3 C4 H4B 109.5 2_665 .
P1 C4 H4B 109.5 . .
H4A C4 H4B 108.1 . .
C10 C5 C6 119.45(18) . .
C10 C5 P1 119.23(15) . .
C6 C5 P1 121.30(15) . .
C7 C6 C5 120.0(2) . .
C7 C6 H6 120.0 . .
C5 C6 H6 120.0 . .
C8 C7 C6 120.0(2) . .
C8 C7 H7 120.0 . .
C6 C7 H7 120.0 . .
C9 C8 C7 120.6(2) . .
C9 C8 H8 119.7 . .
C7 C8 H8 119.7 . .
C8 C9 C10 119.9(2) . .
C8 C9 H9 120.0 . .
C10 C9 H9 120.0 . .
C9 C10 C5 120.0(2) . .
C9 C10 H10 120.0 . .
C5 C10 H10 120.0 . .
C16 C11 C12 117.13(19) . .
C16 C11 N1 121.29(18) . .
C12 C11 N1 121.29(18) . .
C13 C12 C11 120.9(2) . .
C13 C12 H12 119.5 . .
C11 C12 H12 119.5 . .
C12 C13 C14 121.9(2) . .
C12 C13 H13 119.1 . .
C14 C13 H13 119.1 . .
C15 C14 C13 117.0(2) . .
C15 C14 C17 121.2(2) . .
C13 C14 C17 121.8(2) . .
C14 C15 C16 122.2(2) . .
C14 C15 H15 118.9 . .
C16 C15 H15 118.9 . .
C15 C16 C11 120.8(2) . .
C15 C16 H16 119.6 . .
C11 C16 H16 119.6 . .
C14 C17 H17A 109.5 . .
C14 C17 H17B 109.5 . .
H17A C17 H17B 109.5 . .
C14 C17 H17C 109.5 . .
H17A C17 H17C 109.5 . .
H17B C17 H17C 109.5 . .
C19 C18 C23 118.79(17) . .
C19 C18 P2 120.07(14) . .
C23 C18 P2 121.14(14) . .
C20 C19 C18 120.54(19) . .
C20 C19 H19 119.7 . .
C18 C19 H19 119.7 . .
C21 C20 C19 120.36(19) . .
C21 C20 H20 119.8 . .
C19 C20 H20 119.8 . .
C20 C21 C22 119.76(19) . .
C20 C21 H21 120.1 . .
C22 C21 H21 120.1 . .
C23 C22 C21 120.42(18) . .
C23 C22 H22 119.8 . .
C21 C22 H22 119.8 . .
C22 C23 C18 120.12(18) . .
C22 C23 H23 119.9 . .
C18 C23 H23 119.9 . .
F2 B1 F4 109.3(3) . .
F2 B1 F1 110.2(2) . .
F4 B1 F1 110.4(2) . .
F2 B1 F3 108.1(2) . .
F4 B1 F3 108.2(2) . .
F1 B1 F3 110.6(2) . .
N1S C1S C2S 178.7(3) . .
C1S C2S H2S1 109.5 . .
C1S C2S H2S2 109.5 . .
H2S1 C2S H2S2 109.5 . .
C1S C2S H2S3 109.5 . .
H2S1 C2S H2S3 109.5 . .
H2S2 C2S H2S3 109.5 . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Ni1 P1 2.2038(5) .
Ni1 P1 2.2038(5) 2_665
Ni1 P2 2.2163(5) .
Ni1 P2 2.2163(5) 2_665
P1 C5 1.8085(19) .
P1 C4 1.8294(19) .
P1 C1 1.8794(19) .
P2 C18 1.8133(19) .
P2 C3 1.8345(19) .
P2 C2 1.8851(19) 2_665
N1 C11 1.412(3) .
N1 C2 1.441(2) .
N1 C1 1.446(2) .
C1 H1A 0.9900 .
C1 H1B 0.9900 .
C2 P2 1.8851(19) 2_665
C2 H2A 0.9900 .
C2 H2B 0.9900 .
C3 C4 1.527(3) 2_665
C3 H3A 0.9900 .
C3 H3B 0.9900 .
C4 C3 1.527(3) 2_665
C4 H4A 0.9900 .
C4 H4B 0.9900 .
C5 C10 1.393(3) .
C5 C6 1.393(3) .
C6 C7 1.388(3) .
C6 H6 0.9500 .
C7 C8 1.378(3) .
C7 H7 0.9500 .
C8 C9 1.377(3) .
C8 H8 0.9500 .
C9 C10 1.390(3) .
C9 H9 0.9500 .
C10 H10 0.9500 .
C11 C16 1.399(3) .
C11 C12 1.400(3) .
C12 C13 1.387(3) .
C12 H12 0.9500 .
C13 C14 1.388(3) .
C13 H13 0.9500 .
C14 C15 1.380(3) .
C14 C17 1.509(3) .
C15 C16 1.387(3) .
C15 H15 0.9500 .
C16 H16 0.9500 .
C17 H17A 0.9800 .
C17 H17B 0.9800 .
C17 H17C 0.9800 .
C18 C19 1.392(3) .
C18 C23 1.400(3) .
C19 C20 1.387(3) .
C19 H19 0.9500 .
C20 C21 1.377(3) .
C20 H20 0.9500 .
C21 C22 1.387(3) .
C21 H21 0.9500 .
C22 C23 1.385(3) .
C22 H22 0.9500 .
C23 H23 0.9500 .
B1 F2 1.351(3) .
B1 F4 1.371(3) .
B1 F1 1.372(3) .
B1 F3 1.387(3) .
N1S C1S 1.150(4) .
C1S C2S 1.443(5) .
C2S H2S1 0.9800 .
C2S H2S2 0.9800 .
C2S H2S3 0.9800 .
loop_
_cod_related_entry_id
_cod_related_entry_database
_cod_related_entry_code
1 PubChem 168333247
