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_7717799
_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         '2(C30 H36 Cu N14 Zn), 6(B F4), H2 O, C2 H3 N'
_chemical_formula_sum            'C62 H77 B6 Cu2 F24 N29 O Zn2'
_chemical_formula_weight         2023.20
_chemical_name_common
'heterobimetallic cryptate with solvent of crystallisation'
_chemical_name_systematic        '[Zn(II)Cu(I)Li](BF4)3 0.5MeCN 0.5H2O'
_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     iterative
_audit_creation_date             2024-07-04
_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                 96.2500(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.44760(10)
_cell_length_b                   26.5877(2)
_cell_length_c                   24.0965(2)
_cell_measurement_reflns_used    32562
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      72.7270
_cell_measurement_theta_min      3.9010
_cell_volume                     7927.41(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 1.5 (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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(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 0.981
_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    -87.00  -6.00   1.00    1.63    --  -42.17 125.00 120.00   81
  2  \w   -116.00 -18.00   1.00    1.63    --  -42.17 -38.00 -90.00   98
  3  \w     27.00  98.00   1.00    1.63    --   42.17-125.00-180.00   71
  4  \w      6.00  83.00   1.00    1.63    --   42.17 -99.00 150.00   77
  5  \w    103.00 178.00   1.00   25.00    --  104.32  77.00-120.00   75
  6  \w     28.00 137.00   1.00   25.00    --  104.32 -77.00 -60.00  109
  7  \w    103.00 178.00   1.00   25.00    --  104.32  77.00 -60.00   75
  8  \w     97.00 178.00   1.00   25.00    --  104.32 125.00  30.00   81
  9  \w    103.00 178.00   1.00   25.00    --  104.32  77.00-150.00   75
 10  \w     31.00 112.00   1.00   25.00    --  104.32-125.00-120.00   81
 11  \w     75.00 177.00   1.00   25.00    --  104.32  61.00  30.00  102
 12  \w   -115.00 -14.00   1.00    1.63    --  -42.17 -57.00-150.00  101
 13  \w   -116.00 -18.00   1.00    1.63    --  -42.17 -38.00 120.00   98
 14  \w   -115.00 -14.00   1.00    1.63    --  -42.17 -57.00  30.00  101
 15  \w     75.00 177.00   1.00   25.00    --  104.32  61.00-180.00  102
 16  \w     78.00 177.00   1.00   25.00    --  104.32  45.00  90.00   99
 17  \w     76.00 178.00   1.00   25.00    --  104.32  30.00 150.00  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      -0.0334954000
_diffrn_orient_matrix_UB_12      -0.0548038000
_diffrn_orient_matrix_UB_13      0.0096657000
_diffrn_orient_matrix_UB_21      0.0748977000
_diffrn_orient_matrix_UB_22      -0.0010678000
_diffrn_orient_matrix_UB_23      0.0552561000
_diffrn_orient_matrix_UB_31      -0.0936892000
_diffrn_orient_matrix_UB_32      0.0187603000
_diffrn_orient_matrix_UB_33      0.0314381000
_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  0.0636
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            73000
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.884
_diffrn_reflns_theta_min         3.691
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.355
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40945
_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 brownish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.695
_exptl_crystal_description       needle
_exptl_crystal_F_000             4096
_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          0.821
_exptl_crystal_size_mid          0.081
_exptl_crystal_size_min          0.072
_refine_diff_density_max         0.890
_refine_diff_density_min         -1.073
_refine_diff_density_rms         0.107
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1207
_refine_ls_number_reflns         15528
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.150
_refine_ls_R_factor_all          0.0913
_refine_ls_R_factor_gt           0.0850
_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^)+(0.0476P)^2^+48.0666P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1906
_refine_ls_wR_factor_ref         0.1943
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14237
_reflns_number_total             15528
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03161j2.cif
_cod_data_source_block           vs129_needles
_cod_depositor_comments
'Adding full bibliography for 7717799--7717801.cif.'
_cod_database_code               7717799
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         CHNZnCu
_shelx_estimated_absorpt_t_max   0.849
_shelx_estimated_absorpt_t_min   0.248
_reflns_odcompleteness_completeness 99.81
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained planarity
 N400, N300, C640, C700, C6, C5
 with sigma of 0.1
 C240, N700, N800, C270, C26, C25
 with sigma of 0.1
 N700, N800, C270, C26, C25, C240
 with sigma of 0.09
 C15, C16, C170, C140, N120, N110
 with sigma of 0.09
 C5, C6, C700, C640, N300, N400
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
Uanis(N3) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uiso(C34) = Uiso(C340)
Uiso(C370) = Uiso(C37)
Uiso(C540) = Uiso(C54)
Uiso(C570) = Uiso(C57)
Uiso(C44) = Uiso(C440)
Uiso(C47) = Uiso(C470)
Uiso(C27) = Uiso(C270)
Uiso(C24) = Uiso(C240)
Uiso(C640) = Uiso(C4)
Uiso(C700) = Uiso(C7)
Uiso(C17) = Uiso(C170)
Uiso(C14) = Uiso(C140)
4. Others
 Fixed Sof: Zn01(0.85) Cu02(0.85) N11(0.85) C14(0.85) H15(0.85) H15A(0.15)
 H16(0.85) H16A(0.15) C17(0.85) N12(0.85) H8B(0.15) H8A(0.85) H13(0.85)
 H13A(0.15) N8(0.85) C27(0.85) H26(0.85) H26A(0.15) H25(0.85) H25A(0.15)
 C24(0.85) N7(0.85) H28(0.85) H28A(0.15) C700(0.15) H18(0.85) H18A(0.15)
 H3A(0.85) H3B(0.15) N4(0.85) C7(0.85) H6B(0.15) H6A(0.85) H5A(0.85) H5B(0.15)
 C4(0.85) N3(0.85) H23(0.85) H23A(0.15) C640(0.15) Zn03(0.45) Zn04(0.55)
 Cu1(0.45) Cu3(0.55) N250(0.45) N22(0.55) N21(0.55) C44(0.55) H45(0.55)
 H45A(0.45) H46(0.55) H46A(0.45) C47(0.55) N220(0.45) N210(0.45) N260(0.45)
 N170(0.45) N180(0.45) N25(0.55) N26(0.55) C57(0.55) H56(0.55) H56A(0.45)
 H55(0.55) H55A(0.45) C54(0.55) C540(0.45) H58(0.55) H58A(0.45) H53(0.55)
 H53A(0.45) C570(0.45) H43(0.55) H43A(0.45) H33A(0.45) H33(0.55) H48(0.55)
 H48A(0.45) H38A(0.45) H38(0.55) C370(0.45) F63A(0.6) F64A(0.6) F34B(0.4)
 F32B(0.4) F33B(0.4) F34A(0.6) F63B(0.4) F64B(0.4) F32A(0.6) Zn1(0.15)
 Cu2(0.15) N400(0.15) N110(0.15) N300(0.15) N800(0.15) N700(0.15) N120(0.15)
 C340(0.45) C37(0.55) N18(0.55) N17(0.55) C34(0.55) H35A(0.45) H35(0.55)
 H36A(0.45) H36(0.55) C440(0.45) C470(0.45) C270(0.15) C240(0.15) C170(0.15)
 C140(0.15) F33A(0.6)
5.a Free rotating group:
 O1(H1C,H1D)
5.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C22(H22A,H22B), C9(H9A,H9B), C1(H1A,H1B), C19(H19A,H19B),
 C21(H21A,H21B), C20(H20A,H20B), C29(H29A,H29B), C10(H10A,H10B), C30(H30A,H30B),
  C2(H2A,H2B), C11(H11A,H11B), C60(H60A,H60B), C59(H59A,H59B), C39(H39A,H39B),
 C49(H49A,H49B), C40(H40A,H40B), C42(H42A,H42B), C32(H32A,H32B), C51(H51A,H51B),
  C52(H52A,H52B), C41(H41A,H41B), C31(H31A,H31B), C50(H50A,H50B)
5.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C15(H15A), C16(H16), C16(H16A), C8(H8B), C8(H8A), C13(H13),
 C13(H13A), C26(H26), C26(H26A), C25(H25), C25(H25A), C28(H28), C28(H28A),
 C18(H18), C18(H18A), C3(H3A), C3(H3B), C6(H6B), C6(H6A), C5(H5A), C5(H5B),
 C23(H23), C23(H23A), C45(H45), C45(H45A), C46(H46), C46(H46A), C56(H56),
 C56(H56A), C55(H55), C55(H55A), C58(H58), C58(H58A), C53(H53), C53(H53A),
 C43(H43), C43(H43A), C33(H33A), C33(H33), C48(H48), C48(H48A), C38(H38A),
 C38(H38), C35(H35A), C35(H35), C36(H36A), C36(H36)
5.d Fitted hexagon refined as free rotating group:
 N11(C14,C15,C16,C17,N12), N8(C27,C26,C25,C24,N7), N4(C7,C6,C5,C4,N3), N22(N21,
 C44,C45,C46,C47), N25(N26,C57,C56,C55,C54), C37(N18,N17,C34,C35,C36)
5.e Idealised Me refined as rotating group:
 C033(H03A,H03B,H03C)
;
_shelx_res_checksum              82049
_shelx_hkl_checksum              3510
_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 1.696
_oxdiff_exptl_absorpt_empirical_full_min 0.313