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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/4/11/96/4119611.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_4119611
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 Cl2 N2 Ni P4, 2(B F4), 2(C2 H3 N)'
_chemical_formula_sum            'C48 H50 B2 Cl2 F8 N4 Ni P4'
_chemical_formula_weight         1110.03
_chemical_name_common            '[Ni(7PPh2NPhCl)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                105.536(2)
_cell_angle_beta                 91.338(2)
_cell_angle_gamma                117.297(2)
_cell_formula_units_Z            1
_cell_length_a                   10.3125(3)
_cell_length_b                   10.7683(3)
_cell_length_c                   13.0776(6)
_cell_measurement_reflns_used    9910
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      31.96
_cell_measurement_theta_min      2.24
_cell_volume                     1225.11(8)
_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 0.995
_diffrn_measured_fraction_theta_max 0.995
_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  0.0316
_diffrn_reflns_av_sigmaI/netI    0.0381
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            29941
_diffrn_reflns_theta_full        30.51
_diffrn_reflns_theta_max         30.51
_diffrn_reflns_theta_min         2.24
_exptl_absorpt_coefficient_mu    0.706
_exptl_absorpt_correction_T_max  0.9327
_exptl_absorpt_correction_T_min  0.8488
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS; (Sheldrick, 2006)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.505
_exptl_crystal_description       block
_exptl_crystal_F_000             570
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.10
_refine_diff_density_max         1.032
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     314
_refine_ls_number_reflns         7453
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0618
_refine_ls_R_factor_gt           0.0444
_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)+(0.0574P)²+1.0541P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1221
_refine_ls_wR_factor_ref         0.1304
_reflns_number_gt                5756
_reflns_number_total             7453
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja400181a_si_002_4.cif
_cod_data_source_block           helm084
_cod_original_cell_volume        1225.11(7)
_cod_original_sg_symbol_Hall     -P1
_cod_database_code               4119611
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 0.0000 0.5000 0.5000 0.02125(10) Uani 1 2 d S
P1 P -0.10567(6) 0.64000(5) 0.55033(4) 0.02164(12) Uani 1 1 d .
P2 P 0.08290(6) 0.50525(6) 0.65965(4) 0.02249(12) Uani 1 1 d .
Cl1 Cl 0.68656(8) 0.90009(8) 0.63287(7) 0.0547(2) Uani 1 1 d .
N1 N 0.1037(2) 0.79309(19) 0.43936(14) 0.0261(4) Uani 1 1 d .
C1 C -0.2840(2) 0.5480(3) 0.45956(18) 0.0285(4) Uani 1 1 d .
H1A H -0.3600 0.4734 0.4871 0.034 Uiso 1 1 calc R
H1B H -0.3159 0.6211 0.4570 0.034 Uiso 1 1 calc R
C2 C 0.0017(2) 0.8092(2) 0.50819(17) 0.0267(4) Uani 1 1 d .
H2A H -0.0684 0.8273 0.4696 0.032 Uiso 1 1 calc R
H2B H 0.0572 0.8955 0.5732 0.032 Uiso 1 1 calc R
C3 C 0.2699(2) 0.5265(2) 0.65382(17) 0.0271(4) Uani 1 1 d .
H3A H 0.3432 0.6326 0.6764 0.033 Uiso 1 1 calc R
H3B H 0.2926 0.4830 0.7049 0.033 Uiso 1 1 calc R
C4 C -0.0309(3) 0.3133(2) 0.66623(17) 0.0274(4) Uani 1 1 d .
H4A H 0.0340 0.2854 0.7004 0.033 Uiso 1 1 calc R
H4B H -0.1067 0.3112 0.7119 0.033 Uiso 1 1 calc R
C5 C 0.2374(2) 0.8106(2) 0.48620(17) 0.0263(4) Uani 1 1 d .
C6 C 0.3186(3) 0.7530(3) 0.4258(2) 0.0338(5) Uani 1 1 d .
H6 H 0.2781 0.6922 0.3532 0.041 Uiso 1 1 calc R
C7 C 0.4574(3) 0.7834(3) 0.4703(2) 0.0398(6) Uani 1 1 d .
H7 H 0.5124 0.7459 0.4275 0.048 Uiso 1 1 calc R
C8 C 0.5155(3) 0.8677(3) 0.5761(2) 0.0366(5) Uani 1 1 d .
C9 C 0.4388(3) 0.9257(3) 0.6370(2) 0.0403(6) Uani 1 1 d .
H9 H 0.4804 0.9856 0.7097 0.048 Uiso 1 1 calc R
C10 C 0.3007(3) 0.8975(3) 0.5933(2) 0.0369(5) Uani 1 1 d .
H10 H 0.2482 0.9378 0.6367 0.044 Uiso 1 1 calc R
C11 C -0.1450(2) 0.7010(2) 0.68284(17) 0.0248(4) Uani 1 1 d .
C12 C -0.0474(3) 0.8392(2) 0.75471(18) 0.0285(4) Uani 1 1 d .
H12 H 0.0425 0.9008 0.7351 0.034 Uiso 1 1 calc R
C13 C -0.0814(3) 0.8870(3) 0.85463(19) 0.0346(5) Uani 1 1 d .
H13 H -0.0152 0.9821 0.9027 0.042 Uiso 1 1 calc R
C14 C -0.2098(3) 0.7982(3) 0.8849(2) 0.0385(6) Uani 1 1 d .
H14 H -0.2321 0.8317 0.9536 0.046 Uiso 1 1 calc R
C15 C -0.3070(3) 0.6591(3) 0.8145(2) 0.0384(6) Uani 1 1 d .
H15 H -0.3954 0.5971 0.8354 0.046 Uiso 1 1 calc R
C16 C -0.2751(3) 0.6111(3) 0.71395(19) 0.0320(5) Uani 1 1 d .
H16 H -0.3421 0.5165 0.6659 0.038 Uiso 1 1 calc R
C17 C 0.1056(3) 0.6293(2) 0.79230(17) 0.0284(4) Uani 1 1 d .
C18 C 0.2285(3) 0.7701(3) 0.8267(2) 0.0399(6) Uani 1 1 d .
H18 H 0.2959 0.8022 0.7792 0.048 Uiso 1 1 calc R
C19 C 0.2523(4) 0.8629(3) 0.9298(2) 0.0485(7) Uani 1 1 d .
H19 H 0.3361 0.9584 0.9526 0.058 Uiso 1 1 calc R
C20 C 0.1568(4) 0.8188(3) 0.9991(2) 0.0507(8) Uani 1 1 d .
H20 H 0.1756 0.8823 1.0704 0.061 Uiso 1 1 calc R
C21 C 0.0329(4) 0.6817(3) 0.9654(2) 0.0498(7) Uani 1 1 d .
H21 H -0.0351 0.6520 1.0130 0.060 Uiso 1 1 calc R
C22 C 0.0069(3) 0.5867(3) 0.8620(2) 0.0382(5) Uani 1 1 d .
H22 H -0.0787 0.4924 0.8393 0.046 Uiso 1 1 calc R
B1 B 0.2661(3) 0.2309(3) 0.7821(2) 0.0364(6) Uani 1 1 d .
F1 F 0.2919(2) 0.13898(18) 0.82421(15) 0.0543(4) Uani 1 1 d .
F2 F 0.3969(2) 0.3464(2) 0.7773(2) 0.0841(7) Uani 1 1 d .
F3 F 0.1848(2) 0.1543(2) 0.67970(13) 0.0594(5) Uani 1 1 d .
F4 F 0.1892(3) 0.2880(3) 0.84463(17) 0.0863(8) Uani 1 1 d .
C1S C 0.6407(3) 0.3109(3) 0.9054(2) 0.0432(6) Uani 1 1 d .
C2S C 0.5863(4) 0.3610(4) 1.0010(2) 0.0602(9) Uani 1 1 d .
H2S1 H 0.4885 0.3491 0.9798 0.090 Uiso 1 1 calc R
H2S2 H 0.6552 0.4650 1.0387 0.090 Uiso 1 1 calc R
H2S3 H 0.5788 0.3026 1.0488 0.090 Uiso 1 1 calc R
N1S N 0.6844(3) 0.2710(4) 0.8325(2) 0.0586(7) Uani 1 1 d .
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'
Cl Cl 0.1484 0.1585 '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
P2 Ni1 P2 180.00(3) 2_566 .
P2 Ni1 P1 99.962(19) 2_566 2_566
P2 Ni1 P1 80.038(19) . 2_566
P2 Ni1 P1 80.038(19) 2_566 .
P2 Ni1 P1 99.961(19) . .
P1 Ni1 P1 180.0 2_566 .
C11 P1 C1 105.03(10) . .
C11 P1 C2 107.07(10) . .
C1 P1 C2 101.77(10) . .
C11 P1 Ni1 127.14(7) . .
C1 P1 Ni1 106.53(7) . .
C2 P1 Ni1 106.58(7) . .
C17 P2 C3 102.74(10) . .
C17 P2 C4 106.49(10) . .
C3 P2 C4 104.16(10) . .
C17 P2 Ni1 129.30(7) . .
C3 P2 Ni1 106.29(7) . .
C4 P2 Ni1 105.47(7) . .
C5 N1 C2 118.75(18) . .
C5 N1 C4 119.23(18) . 2_566
C2 N1 C4 113.25(18) . 2_566
C3 C1 P1 110.20(15) 2_566 .
C3 C1 H1A 109.6 2_566 .
P1 C1 H1A 109.6 . .
C3 C1 H1B 109.6 2_566 .
P1 C1 H1B 109.6 . .
H1A C1 H1B 108.1 . .
N1 C2 P1 111.69(14) . .
N1 C2 H2A 109.3 . .
P1 C2 H2A 109.3 . .
N1 C2 H2B 109.3 . .
P1 C2 H2B 109.3 . .
H2A C2 H2B 107.9 . .
C1 C3 P2 111.76(14) 2_566 .
C1 C3 H3A 109.3 2_566 .
P2 C3 H3A 109.3 . .
C1 C3 H3B 109.3 2_566 .
P2 C3 H3B 109.3 . .
H3A C3 H3B 107.9 . .
N1 C4 P2 112.18(14) 2_566 .
N1 C4 H4A 109.2 2_566 .
P2 C4 H4A 109.2 . .
N1 C4 H4B 109.2 2_566 .
P2 C4 H4B 109.2 . .
H4A C4 H4B 107.9 . .
C6 C5 C10 117.4(2) . .
C6 C5 N1 121.6(2) . .
C10 C5 N1 120.8(2) . .
C7 C6 C5 120.9(2) . .
C7 C6 H6 119.5 . .
C5 C6 H6 119.5 . .
C8 C7 C6 120.2(2) . .
C8 C7 H7 119.9 . .
C6 C7 H7 119.9 . .
C9 C8 C7 120.1(2) . .
C9 C8 Cl1 119.8(2) . .
C7 C8 Cl1 120.0(2) . .
C8 C9 C10 120.3(2) . .
C8 C9 H9 119.9 . .
C10 C9 H9 119.9 . .
C9 C10 C5 121.0(2) . .
C9 C10 H10 119.5 . .
C5 C10 H10 119.5 . .
C12 C11 C16 119.0(2) . .
C12 C11 P1 120.61(17) . .
C16 C11 P1 120.35(16) . .
C13 C12 C11 120.1(2) . .
C13 C12 H12 119.9 . .
C11 C12 H12 119.9 . .
C14 C13 C12 120.6(2) . .
C14 C13 H13 119.7 . .
C12 C13 H13 119.7 . .
C13 C14 C15 119.8(2) . .
C13 C14 H14 120.1 . .
C15 C14 H14 120.1 . .
C16 C15 C14 120.1(2) . .
C16 C15 H15 120.0 . .
C14 C15 H15 120.0 . .
C15 C16 C11 120.4(2) . .
C15 C16 H16 119.8 . .
C11 C16 H16 119.8 . .
C22 C17 C18 118.8(2) . .
C22 C17 P2 121.79(18) . .
C18 C17 P2 119.33(19) . .
C19 C18 C17 120.1(3) . .
C19 C18 H18 120.0 . .
C17 C18 H18 120.0 . .
C20 C19 C18 120.8(3) . .
C20 C19 H19 119.6 . .
C18 C19 H19 119.6 . .
C19 C20 C21 119.8(2) . .
C19 C20 H20 120.1 . .
C21 C20 H20 120.1 . .
C20 C21 C22 120.4(3) . .
C20 C21 H21 119.8 . .
C22 C21 H21 119.8 . .
C17 C22 C21 120.1(3) . .
C17 C22 H22 120.0 . .
C21 C22 H22 120.0 . .
F2 B1 F1 110.6(2) . .
F2 B1 F4 107.8(3) . .
F1 B1 F4 110.9(3) . .
F2 B1 F3 108.9(3) . .
F1 B1 F3 109.7(2) . .
F4 B1 F3 108.8(2) . .
N1S C1S C2S 178.5(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 P2 2.2140(5) 2_566
Ni1 P2 2.2141(5) .
Ni1 P1 2.2141(5) 2_566
Ni1 P1 2.2141(5) .
P1 C11 1.807(2) .
P1 C1 1.835(2) .
P1 C2 1.888(2) .
P2 C17 1.817(2) .
P2 C3 1.841(2) .
P2 C4 1.879(2) .
Cl1 C8 1.738(3) .
N1 C5 1.405(3) .
N1 C2 1.440(3) .
N1 C4 1.448(3) 2_566
C1 C3 1.530(3) 2_566
C1 H1A 0.9900 .
C1 H1B 0.9900 .
C2 H2A 0.9900 .
C2 H2B 0.9900 .
C3 C1 1.530(3) 2_566
C3 H3A 0.9900 .
C3 H3B 0.9900 .
C4 N1 1.448(3) 2_566
C4 H4A 0.9900 .
C4 H4B 0.9900 .
C5 C6 1.397(3) .
C5 C10 1.399(3) .
C6 C7 1.387(4) .
C6 H6 0.9500 .
C7 C8 1.374(4) .
C7 H7 0.9500 .
C8 C9 1.365(4) .
C9 C10 1.386(4) .
C9 H9 0.9500 .
C10 H10 0.9500 .
C11 C12 1.395(3) .
C11 C16 1.395(3) .
C12 C13 1.386(3) .
C12 H12 0.9500 .
C13 C14 1.375(4) .
C13 H13 0.9500 .
C14 C15 1.392(4) .
C14 H14 0.9500 .
C15 C16 1.384(3) .
C15 H15 0.9500 .
C16 H16 0.9500 .
C17 C22 1.385(4) .
C17 C18 1.397(3) .
C18 C19 1.384(4) .
C18 H18 0.9500 .
C19 C20 1.364(5) .
C19 H19 0.9500 .
C20 C21 1.379(5) .
C20 H20 0.9500 .
C21 C22 1.392(4) .
C21 H21 0.9500 .
C22 H22 0.9500 .
B1 F2 1.370(4) .
B1 F1 1.372(3) .
B1 F4 1.373(4) .
B1 F3 1.377(3) .
C1S N1S 1.130(4) .
C1S C2S 1.454(4) .
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 168333250
