Testing mixed metal bimetallic, and monometallic, cryptates for electrocatalytic hydrogen evolution.
Singh, Varinder; Robb, Matthew G.; Brooker, Sally; Dalton transactions (Cambridge, England : 2003) 54 (2025) 3165–3173; doi:10.1039/d4dt03161j

data_7717800
_publ_section_title
;
 Testing mixed metal bimetallic, and monometallic, cryptates for
 electrocatalytic hydrogen evolution.
;
_journal_issue                   8
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3165
_journal_page_last               3173
_journal_paper_doi               10.1039/d4dt03161j
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C30 H36 Cu N14 Zn, 3(B F4)'
_chemical_formula_sum            'C30 H36 B3 Cu F12 N14 Zn'
_chemical_formula_weight         982.07
_chemical_name_common
'heterobimetallic cryptate (no solvent present)'
_chemical_name_systematic        '[Zn(II)Cu(I)Li](BF4)3'
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-07-04 deposited with the CCDC.	2025-01-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.360(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.2639(4)
_cell_length_b                   14.9629(3)
_cell_length_c                   18.6926(6)
_cell_measurement_reflns_used    11502
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.5750
_cell_measurement_theta_min      3.8340
_cell_volume                     3764.0(2)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (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    -67.00  32.00   1.00    1.00    --  -42.04  38.00  60.00   99
  2  \w    -67.00  32.00   1.00    1.00    --  -42.04  38.00-180.00   99
  3  \w     61.00 131.00   1.00    1.00    --   42.04 178.00   0.00   70
  4  \w     61.00 131.00   1.00    1.00    --   42.04 178.00  90.00   70
  5  \w    103.00 178.00   1.00    2.73    --  104.32  77.00 -30.00   75
  6  \w     31.00 130.00   1.00    2.73    --  104.32 -45.00 -60.00   99
  7  \w    103.00 178.00   1.00    2.73    --  104.32  77.00  60.00   75
  8  \w     28.00 137.00   1.00    2.73    --  104.32 -77.00 -60.00  109
  9  \w    103.00 178.00   1.00    2.73    --  104.32  77.00   0.00   75
 10  \w     75.00 177.00   1.00    2.73    --  104.32  61.00  90.00  102
 11  \w    103.00 178.00   1.00    2.73    --  104.32  77.00  30.00   75
 12  \w   -114.00 -14.00   1.00    1.00    --  -42.04 -57.00 150.00  100
 13  \w   -114.00 -14.00   1.00    1.00    --  -42.04 -57.00  30.00  100
 14  \w   -114.00 -14.00   1.00    1.00    --  -42.04 -57.00 -90.00  100
 15  \w     76.00 178.00   1.00    2.73    --  104.32  30.00-180.00  102
 16  \w     22.00 106.00   1.00    2.73    --  104.32 -95.00 120.00   84
 17  \w     75.00 100.00   1.00    2.73    --  104.32  61.00 -30.00   25
 18  \w     75.00 177.00   1.00    2.73    --  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      0.0121864000
_diffrn_orient_matrix_UB_12      -0.0765346000
_diffrn_orient_matrix_UB_13      0.0577319000
_diffrn_orient_matrix_UB_21      0.0868248000
_diffrn_orient_matrix_UB_22      -0.0382337000
_diffrn_orient_matrix_UB_23      -0.0223108000
_diffrn_orient_matrix_UB_31      0.0736184000
_diffrn_orient_matrix_UB_32      0.0573505000
_diffrn_orient_matrix_UB_33      0.0615158000
_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  0.0422
_diffrn_reflns_av_unetI/netI     0.0326
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            34554
_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         72.649
_diffrn_reflns_theta_min         3.874
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.445
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76626
_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 dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.733
_exptl_crystal_description       block
_exptl_crystal_F_000             1984
_exptl_crystal_preparation       'tested as hydrogen electrocatalyst'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: from MeCN by vapour diffusion of diethylether'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.226
_exptl_crystal_size_min          0.16
_refine_diff_density_max         1.191
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.136
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     663
_refine_ls_number_reflns         7378
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0601
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0443P)^2^+10.8441P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1420
_refine_ls_wR_factor_ref         0.1513
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5896
_reflns_number_total             7378
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03161j2.cif
_cod_data_source_block           vxs168
_cod_depositor_comments
'Adding full bibliography for 7717799--7717801.cif.'
_cod_database_code               7717800
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         CHNZnCuBF
_chemical_oxdiff_usercomment     M622
_shelx_estimated_absorpt_t_max   0.696
_shelx_estimated_absorpt_t_min   0.569
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
2. Restrained planarity
 C5, C400, N300, N400, C700, C6
 with sigma of 0.1
 C16, C140, N120, N130
 with sigma of 0.1
 N130, N120, C140, C15, C16
 with sigma of 0.1
 C270, N800, N16, C240, C25
 with sigma of 0.1
 C14, N12, N13, C17, C16
 with sigma of 0.1
 C4, C5, C6, C7, N4, N3
 with sigma of 0.1
 C5, C6, C700, N400, N300, C400
 with sigma of 0.1
 C15, C16, C170, N130, N120, C140
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
: with sigma of 0.2 and sigma for terminal atoms of 0.2
4. Others
 Fixed Sof: Zn1(0.8) Cu1(0.8) F1(0.8) N4(0.8) N3(0.8) N12(0.8) C700(0.2)
 N8(0.8) H16(0.8) H16A(0.2) C400(0.2) H15(0.8) H15A(0.2) H3B(0.2) H3A(0.8)
 N13(0.8) N9(0.8) H18(0.8) H18A(0.2) H13(0.8) H13A(0.2) H8B(0.2) H8A(0.8)
 H26A(0.2) H26(0.8) F4(0.8) H28A(0.2) H28(0.8) C270(0.2) C14(0.8) H25A(0.2)
 H25(0.8) H23A(0.2) H23(0.8) C240(0.2) H6B(0.2) H6A(0.8) C17(0.8) H5A(0.8)
 H5B(0.2) F3(0.8) Zn2(0.2) Cu2(0.2) N300(0.2) N130(0.2) N400(0.2) N120(0.2)
 N16(0.2) N800(0.2) F400(0.2) F300(0.2) F100(0.2) C170(0.2) C4(0.8) C7(0.8)
 C24(0.8) C27(0.8) C140(0.2)
5.a Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C12(H12A,H12B), C21(H21A,H21B), C30(H30A,H30B), C11(H11A,
 H11B), C19(H19A,H19B), C29(H29A,H29B), C1(H1A,H1B), C9(H9A,H9B), C20(H20A,
 H20B), C10(H10A,H10B), C2(H2A,H2B)
5.b Aromatic/amide H refined with riding coordinates:
 C16(H16), C16(H16A), C15(H15), C15(H15A), C3(H3B), C3(H3A), C18(H18),
 C18(H18A), C13(H13), C13(H13A), C8(H8B), C8(H8A), C26(H26A), C26(H26),
 C28(H28A), C28(H28), C25(H25A), C25(H25), C23(H23A), C23(H23), C6(H6B),
 C6(H6A), C5(H5A), C5(H5B)
;
_shelx_res_checksum              65250
_shelx_hkl_checksum              69890
_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 1.360
_oxdiff_exptl_absorpt_empirical_full_min 0.751