#------------------------------------------------------------------------------
#$Date: 2025-08-21 03:34:05 +0200 (Thu 21 de Aug de 2025) $
#$Revision: 301843 $
#$URL: svn://www.crystallography.net/cod/cif/4/51/67/4516739.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_4516739
loop_
_publ_author_name
'Jeletic, Matthew S.'
'Hulley, Elliott B.'
'Helm, Monte L.'
'Mock, Michael T.'
'Appel, Aaron M.'
'Wiedner, Eric S.'
'Linehan, John C.'
_publ_section_title
;
 Understanding the Relationship Between Kinetics and Thermodynamics in CO2
 Hydrogenation Catalysis
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              6008
_journal_paper_doi               10.1021/acscatal.7b01673
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C24 H38 Co N2 P4, 2(B F4), 2(C2 H3 N)'
_chemical_formula_sum            'C28 H44 B2 Co F8 N4 P4'
_chemical_formula_weight         793.10
_chemical_name_systematic        '[(dmpbz)2Co(CH3CN)2][BF4]2,(CH3CN)2'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-01-11
_audit_creation_method
;
  Olex2 1.2
  (compiled Nov  5 2012 18:25:38, GUI svn.r4372)
;
_audit_update_record
;
2013-01-11 # Formatted by publCIF
;
_cell_angle_alpha                114.987(3)
_cell_angle_beta                 111.721(2)
_cell_angle_gamma                93.719(3)
_cell_formula_units_Z            1
_cell_length_a                   10.0889(5)
_cell_length_b                   10.4012(5)
_cell_length_c                   10.9505(6)
_cell_measurement_reflns_used    7205
_cell_measurement_temperature    140
_cell_measurement_theta_max      30.230
_cell_measurement_theta_min      2.252
_cell_volume                     933.62(9)
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
olex2.solve (L.J. Bourhis, O.V. Dolomanov, R.J. Gildea, J.A.K. Howard,
H. Puschmann, in preparation, 2011)
;
_diffrn_ambient_temperature      140
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0309
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            17485
_diffrn_reflns_theta_full        28.29
_diffrn_reflns_theta_max         28.29
_diffrn_reflns_theta_min         2.24
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9265
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0545 before and 0.0410 after correction.
The Ratio of minimum to maximum transmission is 0.9265.
The λ/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             409
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.640
_refine_diff_density_min         -0.268
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         4572
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0333
_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)+(0.0416P)²+0.3301P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0860
_reflns_number_gt                3747
_reflns_number_total             4572
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            cs7b01673_si_001.cif
_cod_data_source_block           Co(dmpbz)2
_cod_original_cell_volume        933.62(8)
_cod_database_code               4516739
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H4 of C4, H3 of C3, H2 of C2, H5 of C5
 At 1.5 times of:
  {H7A,H7B,H7C} of C7, {H10A,H10B,H10C} of C10, {H9A,H9B,H9C} of C9, {H8A,H8B,
  H8C} of C8, {H13A,H13B,H13C} of C13, {H12A,H12B,H12C} of C12
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C3(H3), C4(H4)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C10(H10A,H10B,H10C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 'x, y, z'
2 '-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
Co1 Co 0.0000 0.5000 0.0000 0.01672(9) Uani 1 2 d S
P1 P -0.07041(5) 0.62294(5) 0.17961(5) 0.01819(11) Uani 1 1 d .
P2 P 0.21215(5) 0.53178(5) 0.18765(5) 0.01817(11) Uani 1 1 d .
C2 C 0.0268(2) 0.6712(2) 0.4779(2) 0.0266(4) Uani 1 1 d .
H2 H -0.0595 0.7029 0.4772 0.032 Uiso 1 1 calc R
C1 C 0.05370(19) 0.62490(18) 0.35157(18) 0.0210(3) Uani 1 1 d .
C6 C 0.1817(2) 0.58050(18) 0.35399(18) 0.0210(3) Uani 1 1 d .
C5 C 0.2829(2) 0.5818(2) 0.4831(2) 0.0259(4) Uani 1 1 d .
H5 H 0.3705 0.5521 0.4855 0.031 Uiso 1 1 calc R
C3 C 0.1278(2) 0.6702(2) 0.6046(2) 0.0304(4) Uani 1 1 d .
H3 H 0.1094 0.7000 0.6903 0.037 Uiso 1 1 calc R
C4 C 0.2551(2) 0.6264(2) 0.6073(2) 0.0305(4) Uani 1 1 d .
H4 H 0.3237 0.6269 0.6949 0.037 Uiso 1 1 calc R
F4 F -0.28166(15) 0.98100(13) 0.65962(14) 0.0450(3) Uani 1 1 d .
F1 F -0.12961(13) 0.84063(15) 0.71160(13) 0.0432(3) Uani 1 1 d .
F2 F -0.37892(15) 0.75078(16) 0.59824(17) 0.0563(4) Uani 1 1 d .
F3 F -0.26326(16) 0.79244(17) 0.47142(14) 0.0555(4) Uani 1 1 d .
C7 C -0.0601(2) 0.81681(19) 0.2397(2) 0.0278(4) Uani 1 1 d .
H7A H 0.0402 0.8691 0.2694 0.042 Uiso 1 1 calc R
H7B H -0.0839 0.8583 0.3253 0.042 Uiso 1 1 calc R
H7C H -0.1309 0.8274 0.1569 0.042 Uiso 1 1 calc R
C10 C 0.2950(2) 0.3790(2) 0.1706(2) 0.0292(4) Uani 1 1 d .
H10A H 0.2221 0.2941 0.1460 0.044 Uiso 1 1 calc R
H10B H 0.3806 0.4072 0.2658 0.044 Uiso 1 1 calc R
H10C H 0.3269 0.3530 0.0909 0.044 Uiso 1 1 calc R
C9 C 0.3642(2) 0.6831(2) 0.2509(2) 0.0272(4) Uani 1 1 d .
H9A H 0.3939 0.6640 0.1705 0.041 Uiso 1 1 calc R
H9B H 0.4481 0.6928 0.3390 0.041 Uiso 1 1 calc R
H9C H 0.3328 0.7744 0.2775 0.041 Uiso 1 1 calc R
C8 C -0.25472(19) 0.5508(2) 0.1523(2) 0.0251(4) Uani 1 1 d .
H8A H -0.3290 0.5646 0.0740 0.038 Uiso 1 1 calc R
H8B H -0.2631 0.6032 0.2464 0.038 Uiso 1 1 calc R
H8C H -0.2711 0.4457 0.1219 0.038 Uiso 1 1 calc R
B1 B -0.2634(2) 0.8400(2) 0.6096(2) 0.0276(4) Uani 1 1 d .
N1 N -0.08657(17) 0.29305(16) 0.00121(16) 0.0244(3) Uani 1 1 d .
C11 C -0.1309(2) 0.19061(19) 0.00311(18) 0.0235(4) Uani 1 1 d .
C12 C -0.1871(2) 0.0606(2) 0.0070(2) 0.0320(4) Uani 1 1 d .
H12A H -0.2100 -0.0272 -0.0879 0.048 Uiso 1 1 calc R
H12B H -0.2771 0.0682 0.0216 0.048 Uiso 1 1 calc R
H12C H -0.1122 0.0533 0.0900 0.048 Uiso 1 1 calc R
C14 C 0.5678(3) 0.9073(3) 0.1759(3) 0.0412(5) Uani 1 1 d .
N2 N 0.5294(3) 0.8251(3) 0.0535(3) 0.0637(6) Uani 1 1 d .
C13 C 0.6153(3) 1.0105(2) 0.3336(3) 0.0454(6) Uani 1 1 d .
H13A H 0.5375 1.0594 0.3450 0.068 Uiso 1 1 calc R
H13B H 0.7059 1.0843 0.3706 0.068 Uiso 1 1 calc R
H13C H 0.6346 0.9575 0.3913 0.068 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'
Co Co 0.3494 0.9721 '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'
N N 0.0061 0.0033 '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'
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 Co1 P1 180.00(3) 2_565 .
P1 Co1 N1 86.77(4) . .
P1 Co1 N1 93.23(4) . 2_565
P1 Co1 N1 93.23(4) 2_565 .
P1 Co1 N1 86.77(4) 2_565 2_565
P2 Co1 P1 85.663(16) . .
P2 Co1 P1 94.337(16) 2_565 .
P2 Co1 P1 94.337(16) . 2_565
P2 Co1 P1 85.663(16) 2_565 2_565
P2 Co1 P2 180.0 . 2_565
P2 Co1 N1 86.80(4) . .
P2 Co1 N1 93.20(4) . 2_565
P2 Co1 N1 93.20(4) 2_565 .
P2 Co1 N1 86.80(4) 2_565 2_565
N1 Co1 N1 180.0 . 2_565
C1 P1 Co1 108.31(6) . .
C7 P1 Co1 118.51(7) . .
C7 P1 C1 102.87(8) . .
C7 P1 C8 102.69(9) . .
C8 P1 Co1 118.49(6) . .
C8 P1 C1 104.05(8) . .
C6 P2 Co1 108.41(6) . .
C10 P2 Co1 119.55(7) . .
C10 P2 C6 103.67(8) . .
C9 P2 Co1 116.33(6) . .
C9 P2 C6 103.02(8) . .
C9 P2 C10 103.98(10) . .
C3 C2 C1 119.22(18) . .
C2 C1 P1 123.02(14) . .
C6 C1 P1 116.81(12) . .
C6 C1 C2 120.16(16) . .
C1 C6 P2 116.94(12) . .
C1 C6 C5 119.80(16) . .
C5 C6 P2 123.19(14) . .
C4 C5 C6 119.80(18) . .
C4 C3 C2 120.71(17) . .
C5 C4 C3 120.31(17) . .
F4 B1 F1 109.57(16) . .
F2 B1 F4 108.26(18) . .
F2 B1 F1 109.95(17) . .
F2 B1 F3 110.46(17) . .
F3 B1 F4 108.69(17) . .
F3 B1 F1 109.87(17) . .
C11 N1 Co1 178.97(15) . .
N1 C11 C12 179.46(19) . .
N2 C14 C13 178.8(3) . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Co1 P1 2.2440(4) .
Co1 P1 2.2440(4) 2_565
Co1 P2 2.2342(4) 2_565
Co1 P2 2.2342(4) .
Co1 N1 2.2771(15) 2_565
Co1 N1 2.2771(15) .
P1 C1 1.8257(18) .
P1 C7 1.8195(18) .
P1 C8 1.8244(18) .
P2 C6 1.8228(17) .
P2 C10 1.8158(19) .
P2 C9 1.8140(18) .
C2 C1 1.397(2) .
C2 C3 1.389(3) .
C1 C6 1.395(3) .
C6 C5 1.399(2) .
C5 C4 1.382(3) .
C3 C4 1.385(3) .
F4 B1 1.384(3) .
F1 B1 1.395(2) .
F2 B1 1.374(3) .
F3 B1 1.380(2) .
N1 C11 1.140(2) .
C11 C12 1.456(3) .
C14 N2 1.133(3) .
C14 C13 1.455(3) .
loop_
_cod_related_entry_id
_cod_related_entry_database
_cod_related_entry_code
1 PubChem 168346232
