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_7713481
_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 H9 Cl3 O6 V, 2(C12 H28 N) 1.6[C4H8O]'
_chemical_formula_sum            'C42 H65 Cl3 N2 O6 V'
_chemical_formula_weight         851.25
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Air-sensitive,Moisture-sensitive
_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             2023-06-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-07-08 deposited with the CCDC.	2023-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.925(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.0922(9)
_cell_length_b                   15.2744(8)
_cell_length_c                   17.8164(9)
_cell_measurement_reflns_used    9215
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      31.08
_cell_measurement_theta_min      2.50
_cell_volume                     5257.9(5)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      110.35
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0666
_diffrn_reflns_av_unetI/netI     0.0179
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            335992
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.268
_diffrn_reflns_theta_min         1.699
_exptl_absorpt_coefficient_mu    0.380
_exptl_absorpt_correction_T_max  0.7465
_exptl_absorpt_correction_T_min  0.6353
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0651 before and 0.0598 after correction.
The Ratio of minimum to maximum transmission is 0.8510.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dark blue'
_exptl_crystal_density_diffrn    1.075
_exptl_crystal_description       plate
_exptl_crystal_F_000             1812
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: HMDSO, THF'
_exptl_crystal_size_max          0.184
_exptl_crystal_size_mid          0.164
_exptl_crystal_size_min          0.158
_refine_diff_density_max         0.543
_refine_diff_density_min         -0.423
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     503
_refine_ls_number_reflns         13015
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.117
_refine_ls_R_factor_all          0.0532
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0712P)^2^+2.9250P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1139
_refine_ls_wR_factor_ref         0.1333
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10638
_reflns_number_total             13015
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01274c2.cif
_cod_data_source_block           complex2_110k
_cod_database_code               7713481
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H00P)=Sof(Cl)=1-FVAR(1)
 Sof(Cl00)=Sof(H00Q)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 N00B(H00B), N00C(H00L)
3.b Secondary CH2 refined with riding coordinates:
 C00L(H00A,H00C), C00Q(H00D,H00E), C00T(H00F,H00G), C00U(H00M,H00N), C00W(H00H,
 H00I), C00Z(H00J,H00K), C011(H01D,H01E), C013(H01R,H01S), C014(H01F,H01G),
 C016(H01T,H01U), C018(H01V,H01W), C019(H01H,H01I), C01A(H01J,H01K), C01B(H01X,
 H01Y), C01C(H01Z,H), C01D(H01,HA), C01G(H2AA,HF), C01L(H4AA,HI)
3.c Aromatic/amide H refined with riding coordinates:
 C00J(H00O), C00K(H00P), C00N(H00Q), C00O(H00R), C00P(H00S), C00R(H00T),
 C00S(H00U), C00V(H00V), C012(H012), C015(H015)
3.d Idealised Me refined as rotating group:
 C010(H01A,H01B,H01C), C01E(H0AA,HB,HC), C01F(H1AA,HD,HE), C01H(H01L,H01M,
 H01N), C01I(H01O,H01P,H01Q), C01K(H3AA,HG,HH)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 67.2 electrons were 
found in a volume of 263.0\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.6[C4H8O] per Formula Unit 
which account for 64 electrons 
per unit cell.
;
_shelx_res_checksum              53467
_shelx_fab_checksum              84756
_olex2_submission_special_instructions 'No special instructions were received'