Nuclear-spin-pattern control of electron-spin dynamics in a series of V(iv) complexes
Jackson, Cassidy E.; Lin, Chun-Yi; Johnson, Spencer H.; van Tol, Johan; Zadrozny, Joseph M.; Chemical Science  (2019) –; doi:10.1039/C9SC02899D

data_1552146
_publ_section_title
;
 Nuclear-spin-pattern control of electron-spin dynamics in a series of
 V(iv) complexes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02899D
_journal_year                    2019
_chemical_formula_moiety         'C18 H6 Br6 O6 V, 2(C12 H28 N)'
_chemical_formula_sum            'C42 H62 Br6 N2 O6 V'
_chemical_formula_weight         1221.33
_chemical_name_common            (n-Bu3NH)2[V(4,5-Br2-C6H2O2)3]
_chemical_name_systematic
'tris(4,5-dibromo-catecholato)vanadate(IV) bis-tri-n-butylammonium'
_chemical_properties_physical    Air-sensitive,Heat-sensitive
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_symmetry_space_group_name_Hall  'P 4nw 2abw'
_symmetry_space_group_name_H-M   'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-06-07 deposited with the CCDC.    2019-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7250(6)
_cell_length_b                   10.7250(6)
_cell_length_c                   42.298(3)
_cell_measurement_reflns_used    9717
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      28.20
_cell_measurement_theta_min      2.69
_cell_volume                     4865.4(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      119.76
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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  0.0872
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            408403
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.679
_diffrn_reflns_theta_min         1.926
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.176
_exptl_absorpt_correction_T_max  0.7043
_exptl_absorpt_correction_T_min  0.6083
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1220 before and 0.1131 after correction. The Ratio of minimum to maximum transmission is 0.8637. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.667
_exptl_crystal_description       Block
_exptl_crystal_F_000             2436
_exptl_crystal_recrystallization_method 'slow evaporation'
_exptl_crystal_size_max          0.156
_exptl_crystal_size_mid          0.154
_exptl_crystal_size_min          0.146
_refine_diff_density_max         0.955
_refine_diff_density_min         -0.694
_refine_diff_density_rms         0.125
_refine_ls_abs_structure_details
;
 Flack x determined using 1744 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.059(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.148
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     259
_refine_ls_number_reflns         4625
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.148
_refine_ls_R_factor_all          0.0525
_refine_ls_R_factor_gt           0.0508
_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^)+(0.0689P)^2^+16.3328P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1459
_refine_ls_wR_factor_ref         0.1500
_reflns_Friedel_coverage         0.666
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4495
_reflns_number_total             4625
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02899d2.cif
_cod_data_source_block           jz29
_cod_original_cell_volume        4865.3(6)
_cod_database_code               1552146
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.519
_shelx_estimated_absorpt_t_min   0.499
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, 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. Restrained distances
 C20-C18
 1.52 with sigma of 0.02
 C20-C18A
 1.52 with sigma of 0.02
3. Others
 Sof(H20C)=Sof(H20D)=Sof(C18A)=Sof(H18C)=Sof(H18D)=Sof(H1AC)=Sof(H1AD)=
 Sof(C1A)=Sof(H1AE)=Sof(H1AF)=Sof(H1AG)=Sof(C5AB)=Sof(H5AD)=Sof(H5AE)=Sof(H5AF)=
 Sof(C4AB)=Sof(H4AC)=Sof(H4AD)=Sof(C2AB)=Sof(H2AC)=Sof(H2AD)=1-FVAR(1)
 Sof(C2AA)=Sof(H2AA)=Sof(H2AB)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H20A)=
 Sof(H20B)=Sof(C4AA)=Sof(H4AA)=Sof(H4AB)=Sof(C5AA)=Sof(H5AA)=Sof(H5AB)=
 Sof(H5AC)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(H1AA)=Sof(H1AB)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 N3(H3)
4.b Secondary CH2 refined with riding coordinates:
 C3AA(H3AA,H3AB), C0AA(H0AA,H0AB), C2AA(H2AA,H2AB), C15(H15A,H15B), C18(H18A,
 H18B), C20(H20A,H20B), C20(H20C,H20D), C4AA(H4AA,H4AB), C6AA(H6AA,H6AB),
 C18A(H18C,H18D), C1AB(H1AA,H1AB), C1AB(H1AC,H1AD), C4AB(H4AC,H4AD), C2AB(H2AC,
 H2AD)
4.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C21(H21)
4.d Idealised Me refined as rotating group:
 C5AA(H5AA,H5AB,H5AC), C7AA(H7AA,H7AB,H7AC), C1(H1A,H1B,H1C), C1A(H1AE,H1AF,
 H1AG), C5AB(H5AD,H5AE,H5AF)
;
_shelx_res_checksum              57686
_olex2_submission_special_instructions 'No special instructions were received'