Impact of Ligand Chlorination and Counterion Tuning on High-Field Spin Relaxation in a Series of V(IV) Complexes
Martinez, Roxanna; Jackson, Cassidy E.; Üngör, Ökten; van Tol, Johan; Zadrozny, Joseph; Dalton Transactions  (2023) –; doi:10.1039/D3DT01274C

data_7713482
_publ_section_title
;
 Impact of Ligand Chlorination and Counterion Tuning on High-Field Spin
 Relaxation in a Series of V(IV) Complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01274C
_journal_year                    2023
_chemical_formula_moiety         'C18 Cl12 O6 V, 2(C12 H28 N)'
_chemical_formula_sum            'C42 H56 Cl12 N2 O6 V'
_chemical_formula_weight         1161.22
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-15
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2022-03-16 deposited with the CCDC.	2023-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                95.5380(10)
_cell_angle_beta                 106.4910(10)
_cell_angle_gamma                95.7900(10)
_cell_formula_units_Z            2
_cell_length_a                   11.54130(10)
_cell_length_b                   12.30200(10)
_cell_length_c                   19.1790(2)
_cell_measurement_reflns_used    37794
_cell_measurement_temperature    99.9(7)
_cell_measurement_theta_max      77.9070
_cell_measurement_theta_min      3.6320
_cell_volume                     2575.27(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (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      99.9(7)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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    -74.00  23.00   0.50    1.60    --  -48.30  90.00 152.00  194
  2  \w      6.00  56.00   0.50    1.60    --   48.30 -90.00  38.00  100
  3  \w   -143.00-118.00   0.50    6.41    --  -86.25 -90.00  38.00   50
  4  \w    -71.00 -46.00   0.50    6.41    --  -86.25  90.00 152.00   50
  5  \w     37.00  86.00   0.50    6.41    --  107.75 -90.00  38.00   98
  6  \w    132.00 157.00   0.50    6.41    --  107.75  90.00 152.00   50
  7  \w    -18.00   8.00   0.50    1.60    --  -48.30  19.00  60.00   52
  8  \w    -41.00  19.00   0.50    1.60    --  -48.30  37.00 150.00  120
  9  \w   -119.00 -75.00   0.50    1.60    --  -48.30-125.00 150.00   88
 10  \w    -42.00  24.00   0.50    1.60    --  -48.30  37.00  90.00  132
 11  \w   -118.00 -89.00   0.50    1.60    --  -48.30-125.00 120.00   58
 12  \w    -24.00  19.00   0.50    1.60    --   48.30 -19.00 120.00   86
 13  \w     38.00 117.00   0.50    1.60    --   48.30  57.00   0.00  158
 14  \w    -50.00 -18.00   0.50    6.41    --  -86.25  45.00 -30.00   64
 15  \w    -50.00 -17.00   0.50    6.41    --  -86.25  45.00   0.00   66
 16  \w     39.00  69.00   0.50    6.41    --  107.75 -77.00  60.00   60
 17  \w     37.00  66.00   0.50    6.41    --  107.75 -61.00 150.00   58
 18  \w     60.00  95.00   0.50    6.41    --  107.75 -75.00  76.87   70
 19  \w    130.00 167.00   0.50    6.41    --  107.75 125.00  30.00   74
 20  \w     50.00  76.00   0.50    6.41    --  107.75 -94.00  90.00   52
 21  \w     38.00  72.00   0.50    6.41    --  107.75 -94.00  30.00   68
 22  \w     43.00  69.00   0.50    6.41    --  107.75-104.00  -6.58   52
 23  \w     46.00 101.00   0.50    6.41    --  107.75 -94.00-120.00  110
 24  \w    136.00 168.00   0.50    6.41    --  107.75  77.00 -90.00   64
 25  \w    146.00 175.00   0.50    6.41    --  107.75  61.00-150.00   58
 26  \w     88.00 132.00   0.50    6.41    --  107.75  77.00 -90.00   88
 27  \w    126.00 167.00   0.50    6.41    --  107.75  30.00-150.00   82
 28  \w     65.00  98.00   0.50    6.41    --  107.75 -94.00-150.00   66
 29  \w     64.00  96.00   0.50    6.41    --  107.75 -77.00 -60.00   64
 30  \w     80.00 106.00   0.50    6.41    --  107.75 -94.00  30.00   52
 31  \w     93.00 119.00   0.50    6.41    --  107.75  63.00-112.50   52
 32  \w    126.00 176.00   0.50    6.41    --  107.75  63.00-112.50  100
 33  \w    104.00 130.00   0.50    6.41    --  107.75  61.00 -30.00   52
 34  \w     39.00  65.00   0.50    6.41    --  107.75 -77.00-150.00   52
 35  \w     81.00 107.00   0.50    6.41    --  107.75-106.00 124.27   52
 36  \w     38.00 108.00   0.50    6.41    --  107.75-107.00 -29.29  140
 37  \w    105.00 155.00   0.50    6.41    --  107.75  30.00 120.00  100
 38  \w     81.00 106.00   0.50    6.41    --  107.75 -94.00 120.00   50
 39  \w    145.00 178.00   0.50    6.41    --  107.75  80.00 -48.49   66
 40  \w    117.00 142.00   0.50    6.41    --  107.75  80.00 -48.49   50
 41  \w     42.00  68.00   0.50    6.41    --  107.75 -94.00 120.00   52
 42  \w     40.00  69.00   0.50    6.41    --  107.75 -61.00 -90.00   58
 43  \w    102.00 128.00   0.50    6.41    --  107.75  81.00 -66.32   52
 44  \w     95.00 141.00   0.50    6.41    --  107.75  61.00-150.00   92
 45  \w    102.00 128.00   0.50    6.41    --  107.75 -85.00 118.70   52
 46  \w     73.00 106.00   0.50    6.41    --  107.75 -94.00-180.00   66
 47  \w     93.00 143.00   0.50    6.41    --  107.75  76.00  98.11  100
 48  \w     72.00 118.00   0.50    6.41    --  107.75 -85.00  -3.28   92
 49  \w    105.00 177.00   0.50    6.41    --  107.75  77.00  30.00  144
 50  \w    103.00 132.00   0.50    6.41    --  107.75  30.00 -90.00   58
 51  \w    139.00 167.00   0.50    6.41    --  107.75  30.00 -90.00   56
 52  \w    110.00 154.00   0.50    6.41    --  107.75  77.00 -60.00   88
 53  \w     86.00 178.00   0.50    6.41    --  107.75  77.00-180.00  184
 54  \w    151.00 177.00   0.50    6.41    --  107.75  30.00-180.00   52
 55  \w     71.00 104.00   0.50    6.41    --  107.75 -94.00  60.00   66
 56  \w     62.00 107.00   0.50    6.41    --  107.75-100.00 -96.83   90
 57  \w     79.00 111.00   0.50    6.41    --  107.75-125.00-180.00   64
 58  \w     66.00  92.00   0.50    6.41    --  107.75-130.00  91.03   52
 59  \w    126.00 173.00   0.50    6.41    --  107.75  45.00  30.00   94
 60  \w    149.00 175.00   0.50    6.41    --  107.75 125.00-180.00   52
 61  \w     82.00 108.00   0.50    6.41    --  107.75-125.00-150.00   52
 62  \w    136.00 162.00   0.50    6.41    --  107.75 104.00  12.49   52
 63  \w    148.00 174.00   0.50    6.41    --  107.75  61.00 -30.00   52
 64  \w     45.00  72.00   0.50    6.41    --  107.75 -83.00 -25.02   54
 65  \w    101.00 131.00   0.50    6.41    --  107.75 -83.00 -25.02   60
 66  \w     37.00  89.00   0.50    6.41    --  107.75 -94.00 -60.00  104
 67  \w     64.00 106.00   0.50    6.41    --  107.75 -94.00 -30.00   84
 68  \w     39.00 106.00   0.50    6.41    --  107.75 -98.00  10.83  134
 69  \w     97.00 132.00   0.50    6.41    --  107.75  30.00-180.00   70
 70  \w    126.00 177.00   0.50    6.41    --  107.75  97.00 132.32  102
 71  \w     77.00 111.00   0.50    6.41    --  107.75-125.00-120.00   68
 72  \w     79.00 108.00   0.50    6.41    --  107.75-125.00 -30.00   58
 73  \w    105.00 138.00   0.50    6.41    --  107.75  45.00  90.00   66
 74  \w    105.00 136.00   0.50    6.41    --  107.75 125.00-150.00   62
 75  \w    142.00 174.00   0.50    6.41    --  107.75 125.00-150.00   64
 76  \w     95.00 154.00   0.50    6.41    --  107.75 125.00-120.00  118
 77  \w    153.00 178.00   0.50    6.41    --  107.75 125.00   0.00   50
 78  \w    101.00 146.00   0.50    6.41    --  107.75 125.00  90.00   90
 79  \w     96.00 136.00   0.50    6.41    --  107.75 125.00 120.00   80
 80  \w    139.00 165.00   0.50    6.41    --  107.75 125.00 150.00   52
 81  \w    143.00 169.00   0.50    6.41    --  107.75  55.00 -71.34   52
 82  \w     94.00 119.00   0.50    6.41    --  107.75  61.00-120.00   50
 83  \w     87.00 113.00   0.50    6.41    --  107.75  77.00 120.00   52
 84  \w     87.00 122.00   0.50    6.41    --  107.75  77.00 150.00   70
 85  \w     42.00  67.00   0.50    6.41    --  107.75 -77.00 150.00   50
 86  \w     36.00  66.00   0.50    6.41    --  107.75 -94.00 150.00   60
;
_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      -0.0436631000
_diffrn_orient_matrix_UB_12      0.1138314000
_diffrn_orient_matrix_UB_13      -0.0070220000
_diffrn_orient_matrix_UB_21      0.0873508000
_diffrn_orient_matrix_UB_22      0.0443348000
_diffrn_orient_matrix_UB_23      0.0767768000
_diffrn_orient_matrix_UB_31      0.1009907000
_diffrn_orient_matrix_UB_32      0.0346075000
_diffrn_orient_matrix_UB_33      -0.0345916000
_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  0.0422
_diffrn_reflns_av_unetI/netI     0.0332
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            60728
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.171
_diffrn_reflns_theta_min         2.424
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.717
_exptl_absorpt_correction_T_max  0.907
_exptl_absorpt_correction_T_min  0.588
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
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            'dark blue'
_exptl_crystal_density_diffrn    1.498
_exptl_crystal_description       block
_exptl_crystal_F_000             1194
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Hexanes, THF'
_exptl_crystal_size_max          0.126
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.054
_refine_diff_density_max         1.236
_refine_diff_density_min         -1.013
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     690
_refine_ls_number_reflns         10949
_refine_ls_number_restraints     876
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0487
_refine_ls_R_factor_gt           0.0441
_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^)+(0.0399P)^2^+2.8170P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1087
_refine_ls_wR_factor_ref         0.1123
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9766
_reflns_number_total             10949
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01274c2.cif
_cod_data_source_block           Complex6_99K
_cod_database_code               7713482
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C41H51Cl12N3O6V
_chemical_oxdiff_usercomment     'Crystallized from THF/HMDSO.'
_shelx_estimated_absorpt_t_max   0.681
_shelx_estimated_absorpt_t_min   0.443
_reflns_odcompleteness_completeness 98.09
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     78.89
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{C38, C37B}
3. Restrained distances
 N1-H1
 0.88 with sigma of 0.02
 N2-H2
 0.83 with sigma of 0.02
 N2B-H2B
 0.83 with sigma of 0.02
 N2-C35 \\sim N2-C31 \\sim N2-C40B \\sim N2B-C39B \\sim N2B-C35B \\sim N2B-C31B
 with sigma of 0.02
 C40-C40B \\sim C39B-C40B \\sim C41-C40 \\sim C31-C32 \\sim C32B-C31B \\sim
C32B-C33 \\sim C32-C33 ~
 C37-C36 \\sim C35B-C36B \\sim C36B-C37B \\sim C37B-C37
 with sigma of 0.02
 C38B-C37B \\sim C33-C34 \\sim C42B-C41B \\sim C41-C42
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C42) = Uanis(C38B)
Uanis(C38) = Uanis(C37B)
5. Rigid body (RIGU) restrains
 C33, C34, C40B, N2, C31, C32, C35, C36, C37, C40, C41, C42, N2B, C31B, C32B,
 C35B, C36B, C37B, C38B, C39B, C41B, C42B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H27C)=Sof(H27D)=Sof(C28B)=Sof(H28C)=Sof(H28D)=Sof(C29B)=Sof(H29C)=
 Sof(H29D)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(H33C)=Sof(H33D)=Sof(H40C)=Sof(H40D)=Sof(N2B)=Sof(H2B)=Sof(C31B)=Sof(H31C)=
 Sof(H31D)=Sof(C32B)=Sof(H32C)=Sof(H32D)=Sof(C35B)=Sof(H35C)=Sof(H35D)=
 Sof(C36B)=Sof(H36C)=Sof(H36D)=Sof(C37B)=Sof(H37C)=Sof(H37D)=Sof(C38B)=
 Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C39B)=Sof(H39A)=Sof(H39B)=Sof(C41B)=
 Sof(H41C)=Sof(H41D)=Sof(C42B)=Sof(H42D)=Sof(H42E)=Sof(H42F)=1-FVAR(2)
 Sof(H33A)=Sof(H33B)=Sof(H40A)=Sof(H40B)=Sof(N2)=Sof(H2)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=
 Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=Sof(H38B)=
 Sof(H38C)=Sof(C40)=Sof(H40E)=Sof(H40F)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=Sof(H42C)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C23(H23A,H23B), C24(H24A,
 H24B), C25(H25A,H25B), C27(H27A,H27B), C27(H27C,H27D), C28(H28A,H28B),
 C29(H29A,H29B), C28B(H28C,H28D), C29B(H29C,H29D), C33(H33A,H33B), C33(H33C,
 H33D), C40B(H40A,H40B), C40B(H40C,H40D), C31(H31A,H31B), C32(H32A,H32B),
 C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C40(H40E,H40F), C41(H41A,H41B),
  C31B(H31C,H31D), C32B(H32C,H32D), C35B(H35C,H35D), C36B(H36C,H36D), C37B(H37C,
 H37D), C39B(H39A,H39B), C41B(H41C,H41D)
7.b Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C26(H26A,H26B,H26C), C30(H30A,H30B,H30C), C30B(H30D,H30E,
 H30F), C34(H34A,H34B,H34C), C38(H38A,H38B,H38C), C42(H42A,H42B,H42C),
 C38B(H38D,H38E,H38F), C42B(H42D,H42E,H42F)
;
_shelx_res_checksum              33458
_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 1.361
_oxdiff_exptl_absorpt_empirical_full_min 0.777