#------------------------------------------------------------------------------
#$Date: 2020-10-06 08:48:16 +0300 (Tue, 06 Oct 2020) $
#$Revision: 257210 $
#$URL: file:///home/coder/svn-repositories/cod/cif/1/55/77/1557724.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_1557724
loop_
_publ_author_name
'Weder, Nicola'
'Probst, Benjamin'
'Sévery, Laurent'
'Fernández-Terán, Ricardo J.'
'Beckord, Jan'
'Blacque, Olivier'
'Tilley, S. David'
'Hamm, Peter'
'Osterwalder, Jürg'
'Alberto, Roger'
_publ_section_title
;
 Mechanistic insights into photocatalysis and over two days of stable H2
 generation in electrocatalysis by a molecular cobalt catalyst immobilized
 on TiO2
;
_journal_issue                   8
_journal_name_full               'Catalysis Science & Technology'
_journal_page_first              2549
_journal_page_last               2560
_journal_paper_doi               10.1039/D0CY00330A
_journal_volume                  10
_journal_year                    2020
_chemical_formula_moiety         'C24 H20 Br2 Co N4 O2, 2(C H4 O)'
_chemical_formula_sum            'C26 H28 Br2 Co N4 O4'
_chemical_formula_weight         679.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-07
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-10-08 deposited with the CCDC.	2020-03-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.751(1)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.0833(1)
_cell_length_b                   11.8214(1)
_cell_length_c                   13.6272(1)
_cell_measurement_reflns_used    16539
_cell_measurement_temperature    160(1)
_cell_measurement_theta_max      78.7740
_cell_measurement_theta_min      4.9410
_cell_volume                     1295.61(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.13a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.13a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.13a (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015b)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      160(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     36.00 124.00   0.50    3.00    --   50.71  57.00 -30.00  176
  2  ω     99.00 178.00   0.50   12.00    --  107.75 111.00-120.00  158
  3  ω     95.00 178.00   0.50   12.00    --  107.75  15.00-120.00  166
  4  ω     95.00 178.00   0.50   12.00    --  107.75  15.00 -60.00  166
  5  ω     95.00 178.00   0.50   12.00    --  107.75  15.00   0.00  166
  6  ω     95.00 178.00   0.50   12.00    --  107.75  15.00-150.00  166
  7  ω     91.00 178.00   0.50   12.00    --  107.75  61.00  30.00  174
  8  ω     94.00 178.00   0.50   12.00    --  107.75  30.00  30.00  168
  9  ω     94.00 178.00   0.50   12.00    --  107.75  30.00 120.00  168
 10  ω     94.00 178.00   0.50   12.00    --  107.75  45.00  30.00  168
 11  ω     94.00 178.00   0.50   12.00    --  107.75  30.00  90.00  168
 12  ω     94.00 178.00   0.50   12.00    --  107.75  30.00  60.00  168
 13  ω     94.00 178.00   0.50   12.00    --  107.75  45.00  60.00  168
 14  ω     92.00 178.00   0.50   12.00    --  107.75  58.00  80.00  172
 15  ω     31.00 108.00   0.50   12.00    --  107.75 -94.00-180.00  154
 16  ω     29.00  69.00   0.50   12.00    --  107.75 -30.00-150.00   80
 17  ω     32.00  77.00   0.50   12.00    --  107.75 -45.00-150.00   90
 18  ω     34.00 130.00   0.50   12.00    --  107.75 -77.00-150.00  192
 19  ω     31.00 115.00   0.50   12.00    --  107.75-111.00-180.00  168
 20  ω     32.00  77.00   0.50   12.00    --  107.75 -45.00-180.00   90
 21  ω     29.00  69.00   0.50   12.00    --  107.75 -30.00 -90.00   80
 22  ω     31.00 108.00   0.50   12.00    --  107.75 -94.00-150.00  154
 23  ω     31.00 115.00   0.50   12.00    --  107.75-111.00 -60.00  168
 24  ω     32.00  77.00   0.50   12.00    --  107.75 -45.00  60.00   90
 25  ω     31.00 115.00   0.50   12.00    --  107.75-111.00  60.00  168
 26  ω     32.00  77.00   0.50   12.00    --  107.75 -45.00 150.00   90
 27  ω     29.00  69.00   0.50   12.00    --  107.75 -30.00 150.00   80
 28  ω     31.00 108.00   0.50   12.00    --  107.75 -94.00  90.00  154
 29  ω     28.00 124.00   0.50    3.00    --   50.71  77.00-120.00  192
 30  ω     28.00 124.00   0.50    3.00    --   50.71  77.00-180.00  192
 31  ω    -63.00  27.00   0.50    3.00    --  -50.71  38.00 -90.00  180
 32  ω    -66.00  22.00   0.50    3.00    --  -50.71  57.00   0.00  176
 33  ω    -63.00  27.00   0.50    3.00    --  -50.71  38.00-180.00  180
 34  ω    -90.00  -9.00   0.50   12.00    --  -86.25 111.00 -30.00  162
 35  ω   -128.00 -39.00   0.50    3.00    --  -50.71 -38.00  30.00  178
 36  ω   -127.00 -82.00   0.50    3.00    --  -50.71 -99.00-120.00   90
 37  ω   -127.00 -82.00   0.50    3.00    --  -50.71 -99.00-180.00   90
 38  ω   -162.00 -73.00   0.50   12.00    --  -86.25 -45.00  60.00  178
 39  ω   -160.00 -72.00   0.50   12.00    --  -86.25 -55.00 105.43  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 200K'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0781732000
_diffrn_orient_matrix_UB_12      0.0724497000
_diffrn_orient_matrix_UB_13      -0.0772511000
_diffrn_orient_matrix_UB_21      -0.1588910000
_diffrn_orient_matrix_UB_22      0.0725191000
_diffrn_orient_matrix_UB_23      -0.0139004000
_diffrn_orient_matrix_UB_31      0.0730712000
_diffrn_orient_matrix_UB_32      0.0804787000
_diffrn_orient_matrix_UB_33      0.0821273000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            26383
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.501
_diffrn_reflns_theta_min         4.963
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.148
_exptl_absorpt_correction_T_max  0.863
_exptl_absorpt_correction_T_min  0.477
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.13a (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.741
_exptl_crystal_description       needle
_exptl_crystal_F_000             682
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.952
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     177
_refine_ls_number_reflns         2644
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0365
_refine_ls_R_factor_gt           0.0345
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[σ²(Fo²)+(0.0513P)²+1.6856P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0928
_refine_ls_wR_factor_ref         0.0942
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2495
_reflns_number_total             2644
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            d0cy00330a2.cif
_cod_data_source_block           Co(II)-9
_cod_depositor_comments
;Adding full bibliography for 1557722--1557724.cif.

 Adding full bibliography for 1557722--1557724.cif.
;
_cod_database_code               1557724
_shelx_shelxl_version_number     2017/1
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_shelx_estimated_absorpt_t_max   0.838
_shelx_estimated_absorpt_t_min   0.305
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 O1-H1 = O2-H2A
 0.82 with sigma of 0.005
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9)
3.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'
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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.62172(4) 0.66795(3) 0.38496(2) 0.03544(13) Uani 1 1 d . . . . .
C1 C 0.6252(3) 0.3145(3) 0.3835(2) 0.0318(6) Uani 1 1 d . . . . .
C2 C 0.7416(4) 0.2307(3) 0.3689(2) 0.0384(7) Uani 1 1 d . . . . .
H2 H 0.720514 0.178672 0.318010 0.046 Uiso 1 1 calc R . . . .
C3 C 0.8869(4) 0.2250(3) 0.4296(3) 0.0417(7) Uani 1 1 d . . . . .
H3 H 0.964989 0.169338 0.420121 0.050 Uiso 1 1 calc R . . . .
C4 C 0.9168(4) 0.3026(3) 0.5051(2) 0.0346(6) Uani 1 1 d . . . . .
H4 H 1.014602 0.299948 0.547282 0.042 Uiso 1 1 calc R . . . .
C5 C 0.7979(3) 0.3843(2) 0.5165(2) 0.0275(6) Uani 1 1 d . . . . .
C6 C 0.8165(3) 0.4714(2) 0.5933(2) 0.0266(5) Uani 1 1 d . . . . .
C7 C 0.9635(4) 0.4912(2) 0.6518(2) 0.0316(6) Uani 1 1 d . . . . .
H7 H 1.057781 0.448177 0.644478 0.038 Uiso 1 1 calc R . . . .
C8 C 0.9670(4) 0.5762(3) 0.7211(2) 0.0366(7) Uani 1 1 d . . . . .
H8 H 1.064651 0.591953 0.760791 0.044 Uiso 1 1 calc R . . . .
C9 C 0.8251(4) 0.6376(3) 0.7312(2) 0.0365(7) Uani 1 1 d . . . . .
H9 H 0.826159 0.694532 0.778315 0.044 Uiso 1 1 calc R . . . .
C10 C 0.6801(4) 0.6143(3) 0.6707(2) 0.0316(6) Uani 1 1 d . . . . .
C11 C 0.5210(4) 0.6742(3) 0.6955(2) 0.0380(7) Uani 1 1 d . . . . .
C12 C 0.4567(4) 0.6083(4) 0.7824(2) 0.0469(8) Uani 1 1 d . . . . .
H12A H 0.543182 0.603872 0.835916 0.070 Uiso 1 1 calc GR . . . .
H12B H 0.424689 0.533341 0.761050 0.070 Uiso 1 1 calc GR . . . .
H12C H 0.362329 0.646896 0.803991 0.070 Uiso 1 1 calc GR . . . .
Co1 Co 0.500000 0.500000 0.500000 0.02586(17) Uani 1 2 d S T P . .
N1 N 0.6764(3) 0.5338(2) 0.60118(17) 0.0269(5) Uani 1 1 d . . . . .
N2 N 0.6520(3) 0.3892(2) 0.45735(17) 0.0272(5) Uani 1 1 d . . . . .
O1 O 0.5643(3) 0.7835(2) 0.7329(2) 0.0505(6) Uani 1 1 d D . . . .
C13 C 0.7110(8) 0.9634(5) 0.5102(4) 0.0810(15) Uani 1 1 d . . . . .
H13A H 0.628181 0.973292 0.455310 0.121 Uiso 1 1 calc GR . . . .
H13B H 0.819235 0.961393 0.486998 0.121 Uiso 1 1 calc GR . . . .
H13C H 0.705406 1.025196 0.555449 0.121 Uiso 1 1 calc GR . . . .
O2 O 0.6819(5) 0.8609(3) 0.5586(3) 0.0735(9) Uani 1 1 d D . . . .
H1 H 0.601(8) 0.808(5) 0.683(3) 0.110 Uiso 1 1 d DR . . . .
H2A H 0.648(8) 0.815(4) 0.516(3) 0.110 Uiso 1 1 d DR . . . .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co -2.3653 3.6143 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0 1 1 0.0201
5 -1 -3 0.0701
-5 1 3 0.0861
0 1 -1 0.0044
0 -1 1 0.0124
0 -1 -1 0.0111
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
_geom_angle_publ_flag
C2 C1 C11 116.6(3) . 3_666 ?
N2 C1 C2 121.0(3) . . ?
N2 C1 C11 121.9(3) . 3_666 ?
C1 C2 H2 120.0 . . ?
C3 C2 C1 119.9(3) . . ?
C3 C2 H2 120.0 . . ?
C2 C3 H3 120.2 . . ?
C2 C3 C4 119.5(3) . . ?
C4 C3 H3 120.2 . . ?
C3 C4 H4 120.8 . . ?
C3 C4 C5 118.4(3) . . ?
C5 C4 H4 120.8 . . ?
C4 C5 C6 123.3(3) . . ?
N2 C5 C4 122.3(3) . . ?
N2 C5 C6 114.4(2) . . ?
C7 C6 C5 123.5(3) . . ?
N1 C6 C5 114.2(2) . . ?
N1 C6 C7 122.3(3) . . ?
C6 C7 H7 120.8 . . ?
C8 C7 C6 118.5(3) . . ?
C8 C7 H7 120.8 . . ?
C7 C8 H8 120.2 . . ?
C9 C8 C7 119.6(3) . . ?
C9 C8 H8 120.2 . . ?
C8 C9 H9 120.1 . . ?
C8 C9 C10 119.9(3) . . ?
C10 C9 H9 120.1 . . ?
C9 C10 C11 117.0(3) . . ?
N1 C10 C9 121.1(3) . . ?
N1 C10 C11 121.5(3) . . ?
C1 C11 C10 119.5(3) 3_666 . ?
C1 C11 C12 106.8(3) 3_666 . ?
C10 C11 C12 106.8(3) . . ?
O1 C11 C1 108.6(3) . 3_666 ?
O1 C11 C10 108.5(3) . . ?
O1 C11 C12 105.8(3) . . ?
C11 C12 H12A 109.5 . . ?
C11 C12 H12B 109.5 . . ?
C11 C12 H12C 109.5 . . ?
H12A C12 H12B 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
Br1 Co1 Br1 180.0 3_666 . ?
N1 Co1 Br1 91.32(7) 3_666 . ?
N1 Co1 Br1 88.68(7) . . ?
N1 Co1 Br1 88.68(7) 3_666 3_666 ?
N1 Co1 Br1 91.32(7) . 3_666 ?
N1 Co1 N1 180.0 . 3_666 ?
N1 Co1 N2 95.28(10) . 3_666 ?
N1 Co1 N2 95.28(10) 3_666 . ?
N1 Co1 N2 84.72(10) 3_666 3_666 ?
N1 Co1 N2 84.72(10) . . ?
N2 Co1 Br1 87.54(7) 3_666 . ?
N2 Co1 Br1 87.54(7) . 3_666 ?
N2 Co1 Br1 92.46(7) . . ?
N2 Co1 Br1 92.46(7) 3_666 3_666 ?
N2 Co1 N2 180.00(10) 3_666 . ?
C6 N1 Co1 113.11(19) . . ?
C10 N1 C6 118.6(2) . . ?
C10 N1 Co1 128.0(2) . . ?
C1 N2 C5 118.8(2) . . ?
C1 N2 Co1 127.94(19) . . ?
C5 N2 Co1 113.05(19) . . ?
C11 O1 H1 96(5) . . ?
H13A C13 H13B 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
O2 C13 H13A 109.5 . . ?
O2 C13 H13B 109.5 . . ?
O2 C13 H13C 109.5 . . ?
C13 O2 H2A 107(5) . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 Co1 2.7707(3) . ?
C1 C2 1.395(4) . ?
C1 C11 1.523(4) 3_666 ?
C1 N2 1.340(4) . ?
C2 H2 0.9300 . ?
C2 C3 1.369(5) . ?
C3 H3 0.9300 . ?
C3 C4 1.381(5) . ?
C4 H4 0.9300 . ?
C4 C5 1.382(4) . ?
C5 C6 1.465(4) . ?
C5 N2 1.362(3) . ?
C6 C7 1.383(4) . ?
C6 N1 1.365(4) . ?
C7 H7 0.9300 . ?
C7 C8 1.377(5) . ?
C8 H8 0.9300 . ?
C8 C9 1.376(5) . ?
C9 H9 0.9300 . ?
C9 C10 1.391(4) . ?
C10 C11 1.535(4) . ?
C10 N1 1.341(4) . ?
C11 C12 1.550(5) . ?
C11 O1 1.420(4) . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?
Co1 N1 1.923(2) 3_666 ?
Co1 N1 1.923(2) . ?
Co1 N2 1.925(2) 3_666 ?
Co1 N2 1.925(2) . ?
O1 H1 0.824(5) . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?
C13 O2 1.410(6) . ?
O2 H2A 0.821(5) . ?
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
O1 H1 O2 0.824(5) 1.976(8) 2.799(5) 177(7) . yes
O2 H2A Br1 0.821(5) 2.484(18) 3.287(3) 166(7) . yes
