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_1552144
_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 H9 Br3 O6 V, 2(C12 H28 N)'
_chemical_formula_sum            'C42 H64 Br3 N2 O6 V'
_chemical_formula_weight         983.62
_chemical_name_common            (n-Bu3NH)2[V(4-Br-C6H3O2)3]
_chemical_name_systematic
'tris(4-bromocatecholato)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   mixed
_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                   14.6090(13)
_cell_length_b                   14.6090(13)
_cell_length_c                   21.144(2)
_cell_measurement_reflns_used    9871
_cell_measurement_temperature    116(2)
_cell_measurement_theta_max      28.14
_cell_measurement_theta_min      2.19
_cell_volume                     4512.6(7)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      116.62
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.900
_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  0.0274
_diffrn_reflns_av_unetI/netI     0.0546
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.900
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            16717
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.851
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.034
_diffrn_reflns_theta_min         1.694
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.921
_exptl_absorpt_correction_T_max  0.7463
_exptl_absorpt_correction_T_min  0.4973
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0783 before and 0.0610 after correction. The Ratio of minimum to maximum transmission is 0.6664. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_description       block
_exptl_crystal_F_000             2024
_exptl_crystal_recrystallization_method 'slow evaporation'
_exptl_crystal_size_max          0.185
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.159
_refine_diff_density_max         0.858
_refine_diff_density_min         -0.615
_refine_diff_density_rms         0.132
_refine_ls_abs_structure_details
;
 Flack x determined using 1639 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.000(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.131
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         5621
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.0566
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0626P)^2^+2.3780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0955
_refine_ls_wR_factor_ref         0.1261
_reflns_Friedel_coverage         0.651
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.784
_reflns_number_gt                4601
_reflns_number_total             5621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02899d2.cif
_cod_data_source_block           jz44_0m_0510
_cod_original_cell_volume        4512.6(9)
_cod_database_code               1552144
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.654
_shelx_estimated_absorpt_t_min   0.614
_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
 C00H-C00H_$1
 1.4 with sigma of 0.02
 C2B-H2B
 0.95 with sigma of 0.02
3. Same fragment restrains
{C1, C2A} sigma for 1-2: 0.02, 1-3: 0.04
as
{C1, C2A}
{C1A, C2B} sigma for 1-2: 0.02, 1-3: 0.04
as
{C2B, C1A}
4. Others
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(H2AC)=Sof(H2AD)=1-FVAR(1)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(H2AA)=Sof(H2AB)=FVAR(1)
 Sof(H00I)=Sof(H00J)=Sof(C0AA)=Sof(H0AA)=Sof(H0AB)=Sof(C00S)=Sof(H00Y)=Sof(H)=
 Sof(HA)=Sof(C00P)=Sof(H00Z)=Sof(HB)=1-FVAR(2)
 Sof(H00G)=Sof(H00H)=Sof(C00O)=Sof(H00R)=Sof(H00S)=Sof(C00Q)=Sof(H00T)=
 Sof(H00U)=Sof(C00R)=Sof(H00V)=Sof(H00W)=Sof(H00X)=FVAR(2)
 Fixed Sof: C1(0.5) H1(0.5) C2A(0.5) C2B(0.5) C1A(0.5) H1A(0.5) Br(0.5) H2B(0.5)
5.a Ternary CH refined with riding coordinates:
 N007(H007)
5.b Secondary CH2 refined with riding coordinates:
 C00C(H00A,H00B), C00D(H00C,H00D), C00F(H00E,H00F), C00I(H00G,H00H), C00I(H00I,
 H00J), C00J(H00K,H00L), C00L(H00P,H00Q), C00O(H00R,H00S), C00Q(H00T,H00U),
 C0AA(H0AA,H0AB), C00P(H00Z,HB), C2AA(H2AA,H2AB), C2AA(H2AC,H2AD)
5.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00), C00B(H1AA), C1(H1), C1A(H1A)
5.d Idealised Me refined as rotating group:
 C00K(H00M,H00N,H00O), C00R(H00V,H00W,H00X), C4(H4A,H4B,H4C), C4A(H4AA,H4AB,
 H4AC), C00S(H00Y,H,HA)
;
_shelx_res_checksum              84296
_olex2_submission_special_instructions 'No special instructions were received'