Asymmetric dinuclear, hexanuclear and octanuclear oxovanadium citrates with triazolates: novel mixed-ligands and mixed-valence complexes.
Xie, Zhen-Lang; Zhou, Zhao-Hui; Dalton transactions (Cambridge, England : 2003) 53 (2023) 186–195; doi:10.1039/d3dt03445c

data_7714514
_publ_section_title
;
 Asymmetric dinuclear, hexanuclear and octanuclear oxovanadium citrates
 with triazolates: novel mixed-ligands and mixed-valence complexes.
;
_journal_issue                   1
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              186
_journal_page_last               195
_journal_paper_doi               10.1039/d3dt03445c
_journal_volume                  53
_journal_year                    2023
_chemical_formula_moiety
'C12 H19 N15 O9 V2, C6 H4 O8 V, 2(C2 H6 N5), 0.5(O), 9[H2O]'
_chemical_formula_sum            'C22 H53 N25 O26.5 V3'
_chemical_formula_weight         1244.71
_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             2023-07-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2023-07-24 deposited with the CCDC.	2023-11-20 downloaded from the CCDC.
;
_cell_angle_alpha                82.025(2)
_cell_angle_beta                 89.802(3)
_cell_angle_gamma                78.306(3)
_cell_formula_units_Z            2
_cell_length_a                   10.4466(4)
_cell_length_b                   10.7317(4)
_cell_length_c                   22.6402(6)
_cell_measurement_reflns_used    7022
_cell_measurement_temperature    233.00(10)
_cell_measurement_theta_max      68.5520
_cell_measurement_theta_min      3.9320
_cell_volume                     2460.67(15)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      233.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.970
_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    -76.00  -7.00   1.00    1.00    --  -40.50 125.00 120.00   69
  2  \w   -113.00 -22.00   1.00    1.00    --  -40.50 -37.00 -60.00   91
  3  \w   -110.00 -18.00   1.00    1.00    --  -40.50 -37.00  30.00   92
  4  \w     43.00  79.00   1.00    1.00    --   42.91-125.00   0.00   36
  5  \w     57.00 112.00   1.00    2.50    --   95.91-125.00 150.00   55
  6  \w    129.00 156.00   1.00    2.50    --   95.91 125.00   0.00   27
  7  \w     19.00  46.00   1.00    2.50    --   95.91 -94.00-150.00   27
  8  \w     29.00 116.00   1.00    2.50    --   95.91 -61.00 120.00   87
  9  \w     77.00 165.00   1.00    2.50    --   95.91  30.00-180.00   88
 10  \w     46.00 118.00   1.00    2.50    --   95.91 -30.00   0.00   72
 11  \w     97.00 137.00   1.00    2.50    --   95.91 125.00  90.00   40
 12  \w     32.00 100.00   1.00    2.50    --   95.91 -94.00 -60.00   68
 13  \w    108.00 161.00   1.00    2.50    --   95.91  77.00-180.00   53
 14  \w     85.00 112.00   1.00    2.50    --   95.91-125.00  60.00   27
 15  \w     69.00 103.00   1.00    2.50    --   95.91 -94.00-150.00   34
 16  \w     28.00 107.00   1.00    2.50    --   95.91 -61.00 -30.00   79
 17  \w     18.00 104.00   1.00    2.50    --   95.91 -15.00-180.00   86
;
_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      -0.1463702000
_diffrn_orient_matrix_UB_12      0.0045792000
_diffrn_orient_matrix_UB_13      0.0110481000
_diffrn_orient_matrix_UB_21      0.0248555000
_diffrn_orient_matrix_UB_22      -0.1477718000
_diffrn_orient_matrix_UB_23      0.0062695000
_diffrn_orient_matrix_UB_31      0.0255311000
_diffrn_orient_matrix_UB_32      -0.0082739000
_diffrn_orient_matrix_UB_33      0.0675480000
_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  0.0507
_diffrn_reflns_av_unetI/netI     0.0652
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            16902
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.908
_diffrn_reflns_theta_min         3.944
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.681
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70497
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.680
_exptl_crystal_description       block
_exptl_crystal_F_000             1282
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.547
_refine_diff_density_min         -0.469
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     668
_refine_ls_number_reflns         8843
_refine_ls_number_restraints     289
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0742
_refine_ls_R_factor_gt           0.0608
_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^)+(0.0456P)^2^+6.4511P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1435
_refine_ls_wR_factor_ref         0.1502
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7295
_reflns_number_total             8843
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt03445c2.cif
_cod_data_source_block           exp_18883_vs-cit-hdatrz_auto
_cod_depositor_comments
'Adding full bibliography for 7714512--7714516.cif.'
_cod_original_formula_sum        'C22 H53 N25 O26.50 V3'
_cod_database_code               7714514
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N V K'
_shelx_estimated_absorpt_t_max   0.600
_shelx_estimated_absorpt_t_min   0.483
_reflns_odcompleteness_completeness 97.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups, All N(H,H) groups
2. Restrained distances
 N21-N22
 1.4 with sigma of 0.02
 C14-C13 = C023-C01W
 2.2 with sigma of 0.02
 N23-C023 = N23-C01W
 1.344 with sigma of 0.02
 N21-C023 = N22-C01W
 1.3 with sigma of 0.02
 N21-N22 = N22A-N21A
 1.4 with sigma of 0.02
 N24-C023 = N24A-C16 = N25-C01W = N25A-C15
 1.31 with sigma of 0.02
 N23-C023 = N23A-C16 = N21-C023 = N21A-C16 = N22-C01W = N22A-C15 = N23-C01W =
 N23A-C15
 1.34 with sigma of 0.02
 N24A-N25A
 4.68 with sigma of 0.02
 C023-C01W
 2.2 with sigma of 0.02
 C16-C15
 2.2 with sigma of 0.02
 N24-N25
 4.68 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N25A \\sim C15 \\sim N22A \\sim N23A \\sim N21A \\sim C16 \\sim N24A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N25 \\sim N22 \\sim N21 \\sim C01W \\sim C023 \\sim N23 \\sim N24: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(N25) \\sim Ueq, Uanis(N22) \\sim Ueq, Uanis(N21) \\sim Ueq, Uanis(C01W)
\\sim Ueq, Uanis(C023) \\sim Ueq, Uanis(N23) \\sim Ueq, Uanis(N24) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N25A) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(N22A) \\sim Ueq, Uanis(N23A)
\\sim Ueq, Uanis(N21A) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(N24A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N25A) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(N23A) \\sim Ueq, Uanis(N22A)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(N21A) \\sim Ueq, Uanis(N24A) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 N23A, N25A, C15, N22A, N21A, C16, N24A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C01W, N22, N21, C023, N25, N23, N24
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(N25A)=Sof(H25C)=Sof(H25D)=Sof(N22A)=Sof(N21A)=Sof(H21C)=Sof(C15)=Sof(C16)=
 Sof(N23A)=Sof(H23A)=Sof(N24A)=Sof(H24C)=Sof(H24D)=1-FVAR(1)
 Sof(N22)=Sof(N21)=Sof(H21)=Sof(C023)=Sof(N23)=Sof(H23)=Sof(C01W)=Sof(N25)=
 Sof(H25A)=Sof(H25B)=Sof(N24)=Sof(H24A)=Sof(H24B)=FVAR(1)
 Fixed Sof: O1W(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C5(H5C,H5D), C18(H18A,H18B), C21(H21A,H21B), C2(H2A,H2B)
6.b Aromatic/amide H refined with riding coordinates:
 N3(H3), N8(H8), N12(H12), N18(H18), N17(H17), N21(H21), N23(H23), N21A(H21C),
 N23A(H23A)
6.c Fitted pentagon refined as free rotating group:
 N22(N21,C023,N23,C01W)
6.d X=CH2 refined with riding coordinates:
 N14(H14A,H14B), N9(H9A,H9B), N4(H4A,H4B), N10(H10A,H10B), N5(H5A,H5B),
 N15(H15A,H15B), N19(H19A,H19B), N20(H20A,H20B), N25(H25A,H25B), N24(H24A,H24B),
  N25A(H25C,H25D), N24A(H24C,H24D)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              85607
_shelx_fab_checksum              69747
_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 1.425
_oxdiff_exptl_absorpt_empirical_full_min 0.741