Synthesis, Crystal Structure, EPR, and DFT Studies of an Unusually Distorted Vanadium(II) Complex
Bonitatibus, Peter John; Alvarez, Santiago; Armstrong, William H.; Baldansuren, Amgalanbaatar; Gaspard, Mallory E.; Lakshmi, K. V.; Ziegler, Micah S.; Charles, Philip; Dalton Transactions  (2022) –; doi:10.1039/D2DT02392J

data_7710869
_publ_section_title
;
 Synthesis, Crystal Structure, EPR, and DFT Studies of an Unusually
 Distorted Vanadium(II) Complex
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT02392J
_journal_year                    2022
_chemical_formula_moiety         'C56 H84 Li2 O8 V, 2(C4 H10 O)'
_chemical_formula_sum            'C64 H104 Li2 O10 V'
_chemical_formula_weight         1098.29
_chemical_name_systematic        'vanadium biphenolate'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-05-06
_audit_creation_method
;
Olex2 1.5-ac5-021
(compiled 2022.02.15 svn.rf212a0ae for Rigaku Oxford Diffraction, GUI svn.r6439)
;
_audit_update_record
;
2022-07-21 deposited with the CCDC.	2022-07-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.9647(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.4271(4)
_cell_length_b                   11.91406(20)
_cell_length_c                   22.8582(4)
_cell_measurement_reflns_used    23718
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      25.3010
_cell_measurement_theta_min      2.2500
_cell_volume                     6345.45(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-021 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-021 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -31.00  12.00   0.50   15.00    --   -4.88 -78.00-104.00   86
  2  \w    -28.00   2.00   0.50   15.00    --   -4.88  78.00  21.00   60
  3  \w    -42.00 -10.00   0.50   15.00    --    5.35 -78.00-104.00   64
  4  \w    -23.00  20.00   0.50   15.00    --   -4.88 -99.00 -30.00   86
  5  \w    -23.00   2.00   0.50   15.00    --   -4.88 -99.00-150.00   50
  6  \w    -22.00  12.00   0.50   15.00    --   -4.88 -99.00  90.00   68
  7  \w    -22.00  35.00   0.50   15.00    --    5.35 -99.00  30.00  114
  8  \w    -19.00  31.00   0.50   15.00    --    5.35 -99.00-180.00  100
  9  \w     -1.00  39.00   0.50   15.00    --    5.35 -99.00 -60.00   80
 10  \w    -14.00  18.00   0.50   15.00    --    5.35 -38.00-180.00   64
 11  \w    -61.00 -17.00   0.50   15.00    --    5.35 -38.00-180.00   88
 12  \w    -67.00 -11.00   0.50   15.00    --    5.35 -38.00  90.00  112
 13  \w    -23.00  30.00   0.50   15.00    --    5.35 -99.00 150.00  106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0212734000
_diffrn_orient_matrix_UB_12      -0.0069461000
_diffrn_orient_matrix_UB_13      0.0196394000
_diffrn_orient_matrix_UB_21      -0.0184357500
_diffrn_orient_matrix_UB_22      0.0370758500
_diffrn_orient_matrix_UB_23      -0.0173812000
_diffrn_orient_matrix_UB_31      -0.0116004000
_diffrn_orient_matrix_UB_32      -0.0460845000
_diffrn_orient_matrix_UB_33      -0.0169062000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0304
_diffrn_reflns_av_unetI/netI     0.0149
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            49894
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.512
_diffrn_reflns_theta_min         2.564
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.210
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.345
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.51a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.150
_exptl_crystal_description       block
_exptl_crystal_F_000             2388
_exptl_crystal_preparation
'vanadium starting material reacted with dithium salt of biphenol ligand in tetrahydrofuran, extracted with diethyl ether'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether'
_exptl_crystal_size_max          0.469
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.096
_refine_diff_density_max         0.415
_refine_diff_density_min         -0.260
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     362
_refine_ls_number_reflns         5911
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0383
_refine_ls_R_factor_gt           0.0347
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0468P)^2^+6.2852P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0922
_refine_ls_wR_factor_ref         0.0943
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5391
_reflns_number_total             5911
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt02392j2.cif
_cod_data_source_block           exp_13a_mo_auto
_cod_original_cell_volume        6345.47(18)
_cod_database_code               7710869
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C64  H104  Li2  O10  V1'
_chemical_oxdiff_usercomment     V-biphenolate
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.908
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C27(H27A,H27B), C34(H34A,H34B), C26(H26A,H26B)
2.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C3(H3)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C14(H14A,H14B,H14C), C16(H16A,H16B,
 H16C), C15(H15A,H15B,H15C), C24(H24A,H24B,H24C), C19(H19A,H19B,H19C), C20(H20A,
 H20B,H20C), C18(H18A,H18B,H18C), C17(H17A,H17B,H17C), C36(H36A,H36B,H36C),
 C38(H38A,H38B,H38C), C28(H28A,H28B,H28C), C25(H25A,H25B,H25C)
;
_olex2_exptl_crystal_mounting_method 'nylon loop'
_olex2_submission_original_sample_id 'vanadium biphenolate'
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.446
_oxdiff_exptl_absorpt_empirical_full_min 0.784