Redox and guest tunable spin-crossover properties in a polymeric polyoxometalate.
Palacios-Corella, Mario; García-López, Víctor; Waerenborgh, Joao Carlos; Vieira, Bruno J. C.; Mínguez Espallargas, Guillermo; Clemente-León, Miguel; Coronado, Eugenio; Chemical science 14 (2023) 3048–3055; doi:10.1039/d2sc05800f

data_1568505
_publ_section_title
;
 Redox and guest tunable spin-crossover properties in a polymeric
 polyoxometalate.
;
_journal_issue                   11
_journal_name_full               'Chemical science'
_journal_page_first              3048
_journal_page_last               3055
_journal_paper_doi               10.1039/d2sc05800f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C32 H29 N12 O21 V6 Zn, Co, 2(C5 H5), 2(O)'
_chemical_formula_sum            'C42 H47 Co N12 O25 V6 Zn'
_chemical_formula_weight         1549.85
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-10-19
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-10-19 deposited with the CCDC.	2023-02-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.569(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0369(18)
_cell_length_b                   27.261(3)
_cell_length_c                   18.467(3)
_cell_measurement_reflns_used    485
_cell_measurement_temperature    119(1)
_cell_measurement_theta_max      16.3510
_cell_measurement_theta_min      4.4220
_cell_volume                     6322.3(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.0267
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
  1 omega  -41.00   49.00   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.7902   57.0000   90.0000 120

  2 omega  -41.00   49.00   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.7902   57.0000  -90.0000 120

  3 omega  -93.00   24.00   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -19.7902  -19.0000  -90.0000 156

  4 omega  -48.00   42.00   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5715  -57.0000    0.0000 120

  5 omega   -1.00   89.00   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5715   57.0000  150.0000 120

  6 omega   -9.00   42.00   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5715   77.0000  -30.0000 68

  7 omega   -5.00   92.50   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5715   38.0000  120.0000 130

  8 omega    8.00   80.00   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5715 -128.0000 -148.8772 96

  9 omega   -1.00   89.00   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5715   57.0000 -120.0000 120

 10 omega    5.00   78.50   0.7500   40.0000
omega____ theta____ kappa____ phi______ frames
    -       22.0000 -124.0000   22.8856 98
;
_diffrn_measurement_device_type
'SuperNova, Single source at offset), Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.3572
_diffrn_reflns_av_unetI/netI     0.1714
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            41118
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        17.255
_diffrn_reflns_theta_max         17.255
_diffrn_reflns_theta_min         3.225
_exptl_absorpt_coefficient_mu    1.558
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76264
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.628
_exptl_crystal_description       needle
_exptl_crystal_F_000             3112
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.832
_refine_diff_density_min         -1.036
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         3821
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.1950
_refine_ls_R_factor_gt           0.1281
_refine_ls_shift/su_max          0.002
_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          0.3164
_refine_ls_wR_factor_ref         0.3634
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2135
_reflns_number_total             3821
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05800f2.cif
_cod_data_source_block           polznred1_2
_cod_depositor_comments
'Adding full bibliography for 1568503--1568506.cif.'
_cod_original_cell_volume        6322.5(16)
_cod_database_code               1568505
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.912
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 C11C-Co1
 2.095 with sigma of 0.01
 Co1-C15C
 2.095 with sigma of 0.01
 Co1-C14C
 2.095 with sigma of 0.01
 Co1-C13C
 2.095 with sigma of 0.01
 Co1-C12C
 2.095 with sigma of 0.01
 C17C-Co1
 2.095 with sigma of 0.02
 C18C-Co1
 2.095 with sigma of 0.02
 C20C-Co1
 2.095 with sigma of 0.02
 C16C-Co1
 2.095 with sigma of 0.02
 Co1-C19C
 2.095 with sigma of 0.02
 C11C-C16C
 3.5 with sigma of 0.02
 C15C-C20C
 3.5 with sigma of 0.02
 C14C-C19C
 3.5 with sigma of 0.02
 C12C-C17C
 3.5 with sigma of 0.02
 C13C-C18C
 3.5 with sigma of 0.02
3. Rigid bond restraints
 C17C, C16C, C20C, C19C, C18C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C11C, C12C, C13C, C14C, C15C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C25C, C24C, C23C, C22C, C21C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C17C \\sim C16C \\sim C20C \\sim C19C \\sim C18C: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C11C \\sim C12C \\sim C13C \\sim C14C \\sim C15C: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
C25C \\sim C24C \\sim C23C \\sim C22C \\sim C21C: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
5. Others
 Fixed Sof: Co1(0.5) C11C(0.5) H11C(0.5) C12C(0.5) H12C(0.5) C13C(0.5)
 H13C(0.5) C14C(0.5) H14C(0.5) C15C(0.5) H15C(0.5) C17C(0.5) H17C(0.5)
 C16C(0.5) H16C(0.5) C20C(0.5) H20C(0.5) C19C(0.5) H19C(0.5) C18C(0.5) H18C(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C51(H51A,H51B), C52(H52A,
 H52B), C53(H53A,H53B)
6.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C10(H10), C11(H11), C14(H14), C15(H15), C16(H16), N19(H19),
 C33(H33), C35(H35), C41(H41), C40(H40), C39(H39), C44(H44), C45(H45), C46(H46),
  N49(H49), C11C(H11C), C12C(H12C), C13C(H13C), C14C(H14C), C15C(H15C),
 C17C(H17C), C16C(H16C), C20C(H20C), C19C(H19C), C18C(H18C), C25C(H25C),
 C24C(H24C), C23C(H23C), C22C(H22C), C21C(H21C)
6.c Fitted pentagon refined as free rotating group:
 N37(C41,C40,C39,N38), C11C(C12C,C13C,C14C,C15C), C17C(C16C,C20C,C19C,C18C),
 C25C(C24C,C23C,C22C,C21C)
6.d Fitted hexagon refined as free rotating group:
 N1(C6,C5,C4,C3,C2), C34(C33,C32,N31,C36,C35)
;
_shelx_res_checksum              22271
_shelx_hkl_checksum              61232
_shelx_fab_checksum              66366
_olex2_submission_special_instructions 'No special instructions were received'