Synthesis, structure and spectroelectrochemistry of hybrid metal(iv)phthalocyaninato-capped 3d-metal pyrazoloximates as prospective precursors of stimuli-induced (responsive) single-molecule magnets, logic gates and qubits
Belova, Svetlana A.; Dudkin, Semyon V.; Belov, Alexander S.; Danshina, Anastasia A.; Dorovatovskii, Pavel V.; Budnikova, Yulia H.; Khrizanforova, Vera V.; Bratskaya, Svetlana Yu.; Balatskiy, Denis V.; Voloshin, Yan Z.; New Journal of Chemistry 48 (2024) 17831–17848; doi:10.1039/D4NJ02908A

data_7063450
_publ_section_title
;
 Synthesis, structure and spectroelectrochemistry of hybrid
 metal(iv)phthalocyaninato-capped 3d-metal pyrazoloximates as prospective
 precursors of stimuli-induced (responsive) single-molecule magnets, logic
 gates and qubits
;
_journal_issue                   41
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              17831
_journal_page_last               17848
_journal_paper_doi               10.1039/D4NJ02908A
_journal_volume                  48
_journal_year                    2024
_chemical_formula_moiety         'C94 H62 Co3 N34 O6 Zr2, 6(C H Cl3), 1[CHCl3]'
_chemical_formula_sum            'C101 H69 Cl21 Co3 N34 O6 Zr2'
_chemical_formula_weight         2958.58
_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
_audit_creation_date             2024-08-21
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-21 deposited with the CCDC.	2024-09-25 downloaded from the CCDC.
;
_cell_angle_alpha                84.63(3)
_cell_angle_beta                 76.91(3)
_cell_angle_gamma                79.80(3)
_cell_formula_units_Z            1
_cell_length_a                   12.541(3)
_cell_length_b                   13.436(3)
_cell_length_c                   17.462(4)
_cell_measurement_reflns_used    24317
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30
_cell_measurement_theta_min      3
_cell_volume                     2816.2(12)
_computing_cell_refinement       'iMosflm (Battye et al., 2011)'
_computing_data_collection       'Marccd (Doyle, 2011)'
_computing_data_reduction        'iMosflm (Battye et al., 2011)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.946
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_device_type
'MarExperts mardtb goniostat and Rayonix SX 165 detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.745
_diffrn_reflns_av_R_equivalents  0.1097
_diffrn_reflns_av_unetI/netI     0.1370
_diffrn_reflns_Laue_measured_fraction_full 0.946
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            20552
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        26.551
_diffrn_reflns_theta_max         26.499
_diffrn_reflns_theta_min         1.257
_exptl_absorpt_coefficient_mu    1.340
_exptl_absorpt_correction_T_max  0.990
_exptl_absorpt_correction_T_min  0.942
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1162 before and 0.1097 after correction.
The Ratio of minimum to maximum transmission is 0.7094.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.744
_exptl_crystal_description       plate
_exptl_crystal_F_000             1479
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.01
_refine_diff_density_max         4.530
_refine_diff_density_min         -1.522
_refine_diff_density_rms         0.313
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.488
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     691
_refine_ls_number_reflns         9626
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.483
_refine_ls_R_factor_all          0.2000
_refine_ls_R_factor_gt           0.1531
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4001
_refine_ls_wR_factor_ref         0.4304
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5872
_reflns_number_total             9626
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj02908a3.cif
_cod_data_source_block           ss226_zr_co_co_co_zr
_cod_depositor_comments
'Adding full bibliography for 7063450--7063453.cif.'
_cod_original_cell_volume        2816.3(11)
_cod_database_code               7063450
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.912
_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
2. Uiso/Uaniso restraints and constraints
Uanis(C50) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C16) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C40) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N15) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N5) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N2) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C17) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(N2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C28) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C12) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O2) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(N12) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C48(H48), C49(H49), C50(H50)
3.b Aromatic/amide H refined with riding coordinates:
 C37(H37), C36(H36), C35(H35), C34(H34), C42(H42), C43(H43), C44(H44),
 C45(H45), C26(H26), C27(H27), C28(H28), C29(H29), C19(H19), C20(H20), C21(H21),
  C18(H18), C13(H13), C3(H3), C14(H14), C8(H8), C9(H9), C4(H4)
3.c Fitted hexagon refined as free rotating group:
 C33(C38,C37,C36,C35,C34), C46(C41,C42,C43,C44,C45), C25(C26,C27,C28,C29,C30),
 C19(C20,C21,C22,C17,C18)
3.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C15(H15A,H15B,H15C), C10(H10A,H10B,H10C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 56 electrons were 
found in a volume of 230\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[CHCl3] per formula unit 
which account for 58 electrons 
per unit cell.
;
_shelx_res_checksum              84590
_shelx_hkl_checksum              21752
_shelx_fab_checksum              20733
_olex2_submission_special_instructions 'No special instructions were received'