Mono-copper far more active than analogous di-copper complex for electrocatalytic hydrogen evolution.
Singh, Varinder; Abudayyeh, Abdullah M.; Robb, Matthew G.; Brooker, Sally; Dalton transactions (Cambridge, England : 2003) 51 (2022) 4166–4172; doi:10.1039/d2dt00141a

data_7709486
_publ_section_title
;
 Mono-copper far more active than analogous di-copper complex for
 electrocatalytic hydrogen evolution.
;
_journal_issue                   10
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4166
_journal_page_last               4172
_journal_paper_doi               10.1039/d2dt00141a
_journal_volume                  51
_journal_year                    2022
_chemical_formula_moiety         'C44 H44 Cu2 N8, 2(C2 H3 N), 2(B F4)'
_chemical_formula_sum            'C48 H50 B2 Cu2 F8 N10'
_chemical_formula_weight         1067.68
_chemical_name_common
'dicopper(II) complex of orthophenylene linked macrocycles'
_chemical_name_systematic        VSX185
_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     dual
_audit_creation_date             2022-01-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-01-13 deposited with the CCDC.	2022-02-15 downloaded from the CCDC.
;
_cell_angle_alpha                77.963(2)
_cell_angle_beta                 84.825(2)
_cell_angle_gamma                81.221(2)
_cell_formula_units_Z            2
_cell_length_a                   9.3827(2)
_cell_length_b                   13.8186(4)
_cell_length_c                   18.5659(5)
_cell_measurement_reflns_used    18516
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.7230
_cell_measurement_theta_min      3.6570
_cell_volume                     2322.42(11)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3449
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -70.00  31.00   1.00    1.00    --  -42.17  57.00-180.00  101
  2  \w    -87.00  -6.00   1.00    1.00    --  -42.17 125.00 -60.00   81
  3  \w   -115.00 -14.00   1.00    1.00    --  -42.17 -57.00  30.00  101
  4  \w    -21.00  75.00   1.00    1.00    --   42.17 -77.00 -90.00   96
  5  \w     31.00 130.00   1.00    1.00    --  104.32 -45.00-150.00   99
  6  \w    103.00 178.00   1.00    1.00    --  104.32  77.00 120.00   75
  7  \w     28.00 137.00   1.00    1.00    --  104.32 -77.00 150.00  109
  8  \w     22.00 106.00   1.00    1.00    --  104.32 -95.00  90.00   84
  9  \w     32.00 133.00   1.00    1.00    --  104.32 -61.00   0.00  101
 10  \w     28.00 133.00   1.00    1.00    --  104.32 -30.00  90.00  105
 11  \w     28.00 133.00   1.00    1.00    --  104.32 -30.00 -30.00  105
 12  \w     31.00 112.00   1.00    1.00    --  104.32-125.00 -90.00   81
 13  \w     31.00 112.00   1.00    1.00    --  104.32-125.00 -30.00   81
 14  \w     22.00 106.00   1.00    1.00    --  104.32 -95.00   0.00   84
 15  \w     22.00 106.00   1.00    1.00    --  104.32 -95.00 -30.00   84
 16  \w     16.00 178.00   1.00    1.00    --  104.32   0.00 120.00  162
 17  \w   -115.00 -14.00   1.00    1.00    --  -42.17 -57.00-150.00  101
 18  \w      8.00  42.00   1.00    1.00    --   42.17  82.00 -56.72   34
 19  \w      9.00  42.00   1.00    1.00    --   42.17  81.00-131.98   33
 20  \w      8.00  42.00   1.00    1.00    --   42.17  82.00 173.96   34
 21  \w     75.00 177.00   1.00    1.00    --  104.32  61.00   0.00  102
 22  \w     76.00 177.00   1.00    1.00    --  104.32  56.00 -35.40  101
 23  \w     75.00 177.00   1.00    1.00    --  104.32  61.00-180.00  102
 24  \w     73.00 178.00   1.00    1.00    --  104.32  70.00 127.69  105
 25  \w     52.00 178.00   1.00    1.00    --  104.32  15.00 -60.00  126
 26  \w     75.00 177.00   1.00    1.00    --  104.32  61.00 -66.68  102
 27  \w     75.00 177.00   1.00    1.00    --  104.32  61.00  30.00  102
 28  \w     73.00 178.00   1.00    1.00    --  104.32  70.00-122.70  105
 29  \w     75.00 177.00   1.00    1.00    --  104.32  61.00  60.00  102
 30  \w     75.00 177.00   1.00    1.00    --  104.32  61.00  90.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0251559000
_diffrn_orient_matrix_UB_12      0.0274416000
_diffrn_orient_matrix_UB_13      0.0768591000
_diffrn_orient_matrix_UB_21      -0.0571592000
_diffrn_orient_matrix_UB_22      -0.1001165000
_diffrn_orient_matrix_UB_23      0.0311969000
_diffrn_orient_matrix_UB_31      0.1542816000
_diffrn_orient_matrix_UB_32      -0.0496748000
_diffrn_orient_matrix_UB_33      0.0185533000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            42909
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.821
_diffrn_reflns_theta_min         3.696
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.816
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68884
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.527
_exptl_crystal_description       block
_exptl_crystal_F_000             1096
_exptl_crystal_preparation
'electrocatalysis; hydrogen production; proton reduction'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: MeCN by vapour diffusion of diethylether'
_exptl_crystal_size_max          0.484
_exptl_crystal_size_mid          0.215
_exptl_crystal_size_min          0.102
_refine_diff_density_max         0.848
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     668
_refine_ls_number_reflns         9116
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0521
_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
'w=1/[\s^2^(Fo^2^)+(0.0557P)^2^+2.9050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1094
_refine_ls_wR_factor_ref         0.1168
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7719
_reflns_number_total             9116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00141a2.cif
_cod_data_source_block           vxs185
_cod_depositor_comments          'Adding full bibliography for 7709486.cif.'
_cod_database_code               7709486
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNCuBF
_chemical_oxdiff_usercomment     M649
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.474
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Same fragment restrains
{B1, F11, F12, F13, F14} sigma for 1-2: 0.02, 1-3: 0.04
as in
{B3, F31, F32, F33, F34}
{B1, F11, F12, F13, F14} sigma for 1-2: 0.02, 1-3: 0.04
as in
{B2, F21, F22, F23, F24}
3. Others
 Fixed Sof: B2(0.85) F21(0.85) F22(0.85) F23(0.85) F24(0.85) B3(0.15)
 F31(0.15) F32(0.15) F33(0.15) F34(0.15)
4.a Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C19(H19A,H19B), C17(H17A,H17B), C18(H18A,H18B), C27(H27A,
 H27B), C43(H43A,H43B), C44(H44A,H44B), C2(H2A,H2B), C1(H1A,H1B), C28(H28A,H28B)
4.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C22(H22), C8(H8), C24(H24), C21(H21), C42(H42), C11(H11), C5(H5),
 C3(H3), C16(H16), C37(H37), C38(H38), C6(H6), C34(H34), C40(H40), C29(H29),
 C39(H39), C7(H7), C12(H12), C14(H14), C33(H33), C13(H13), C32(H32), C31(H31)
4.c Idealised Me refined as rotating group:
 C470(H47A,H47B,H47C), C450(H45A,H45B,H45C)
;
_shelx_res_checksum              2766
_shelx_hkl_checksum              70455
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.216
_oxdiff_exptl_absorpt_empirical_full_min 0.723