Vanadium(V) Complexes with Substituted 1,5-bis(2-hydroxybenzaldehyde)carbohydrazones and Their Use As Catalyst Precursors in Oxidation of Cyclohexane.
Dragancea, Diana; Talmaci, Natalia; Shova, Sergiu; Novitchi, Ghenadie; Darvasiová, Denisa; Rapta, Peter; Breza, Martin; Galanski, Markus; Kož\?íšek, Jozef; Martins, Nuno M. R.; Martins, Luísa M D R S; Pombeiro, Armando J. L.; Arion, Vladimir B.; Inorganic chemistry 55 (2016) 9187–9203; doi:10.1021/acs.inorgchem.6b01011

data_4348139
_publ_section_title
;
 Vanadium(V) Complexes with Substituted
 1,5-bis(2-hydroxybenzaldehyde)carbohydrazones and Their Use As Catalyst
 Precursors in Oxidation of Cyclohexane.
;
_journal_issue                   18
_journal_name_full               'Inorganic chemistry'
_journal_page_first              9187
_journal_page_last               9203
_journal_paper_doi               10.1021/acs.inorgchem.6b01011
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety
'C32.75 H23.5 Cl8 N8 O15 V4, 0.75(H2 O), 3.55(C H4 O)'
_chemical_formula_sum            'C36.3 H39.2 Cl8 N8 O19.3 V4'
_chemical_formula_weight         1383.72
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-03-07
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                104.222(4)
_cell_angle_beta                 91.701(3)
_cell_angle_gamma                103.923(4)
_cell_formula_units_Z            2
_cell_length_a                   12.4787(15)
_cell_length_b                   14.6106(15)
_cell_length_c                   15.592(2)
_cell_measurement_reflns_used    3916
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      27.413
_cell_measurement_theta_min      2.497
_cell_volume                     2662.7(5)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      120.0
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker X8 APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0405
_diffrn_reflns_av_unetI/netI     0.0698
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            18056
_diffrn_reflns_theta_full        25.03
_diffrn_reflns_theta_max         25.03
_diffrn_reflns_theta_min         1.73
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    1.160
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6808
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1726 before and 0.0442 after correction.
The Ratio of minimum to maximum transmission is 0.9126.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.726
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1391
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.294
_refine_diff_density_min         -1.042
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     648
_refine_ls_number_reflns         9353
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0886
_refine_ls_R_factor_gt           0.0608
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0603P)^2^+11.4662P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1431
_refine_ls_wR_factor_ref         0.1599
_reflns_number_gt                6833
_reflns_number_total             9353
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic6b01011_si_004.cif
_cod_data_source_block           ando167_2m_p-1
_cod_original_formula_sum        'C36.30 H39.20 Cl8 N8 O19.30 V4'
_cod_database_code               4348139
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H11,H11A} of C11, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, {H1WA,H1WB} of C14X, All O(H) groups, All O(H,H) groups
2. Restrained distances
 V2-H5A
 2.935053 with sigma of 0.02
 C38-H5A
 2.001334 with sigma of 0.02
 Cl3X-C14X \\sim Cl3-C14 \\sim Cl4X-C12X \\sim Cl4-C12
 with sigma of 0.01
 O3-C15X \\sim O3-C15
 with sigma of 0.01
 O16-C36 \\sim O18-C35
 with sigma of 0.01
 Cl8X-C27X \\sim Cl8-C27 \\sim Cl7X-C29X \\sim Cl7-C29
 with sigma of 0.01
 O18-C35 \\sim O16-C36 \\sim O19_$2-C40_$2 \\sim O5_$1-C38_$1 \\sim
O21_$3-C34_$3 \\sim O17_$3-
 C39_$3
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(Cl8X) = Uanis(Cl8) = Uanis(Cl7X) = Uanis(Cl7)
Uiso(C15X) = Uiso(C13) = Uiso(C14) = Uiso(C14X) = Uiso(C13X) = Uiso(C15) =
Uiso(C12X) = Uiso(C12)
Uanis(Cl3X) = Uanis(Cl3) = Uanis(Cl4X) = Uanis(Cl4)
Uanis(Cl1) = Uanis(Cl1X)
Uiso(C40) = Uiso(O19) = Uiso(O2W)
Uiso(O18) = Uiso(O16) = Uiso(C36) = Uiso(C35)
Uiso(C29X) = Uiso(C26) = Uiso(C27) = Uiso(C28X) = Uiso(C26X) = Uiso(C27X) =
Uiso(C28) = Uiso(C29)
4. Others
 Fixed Sof: Cl1(0.5) Cl1X(0.5) Cl3(0.5) Cl3X(0.5) Cl4(0.5) Cl4X(0.5) Cl7(0.5)
 Cl7X(0.5) Cl8(0.5) Cl8X(0.5) H5B(0.25) C12(0.5) C13(0.5) H13(0.5) C13X(0.5)
 H13X(0.5) C12X(0.5) H11(0.5) H11A(0.5) C15X(0.5) C14X(0.5) H1WA(0.25)
 H1WB(0.25) C14(0.5) C15(0.5) C26(0.5) H26(0.5) C27(0.5) C27X(0.5) C26X(0.5)
 H26X(0.5) C29X(0.5) C28X(0.5) H28X(0.5) C28(0.5) H28(0.5) C29(0.5) C38(0.75)
 H38A(0.75) H38B(0.75) H38C(0.75) O19(0.5) H19(0.5) C40(0.5) H40B(0.5)
 H40C(0.5) H40A(0.5) O18(0.4) H18A(0.4) C35(0.4) H35A(0.4) H35B(0.4) H35C(0.4)
 O16(0.4) H16(0.4) C36(0.4) H36A(0.4) H36C(0.4) H36B(0.4) O20(0.25) H20A(0.25)
 C37(0.25) H37A(0.25) H37B(0.25) H37C(0.25) O1W(0.25) O2W(0.5) H2WA(0.5)
 H2WB(0.5)
5.a Riding coordinates:
 O5(H5A,H5B), C14X(H1WA,H1WB), C26(H26), C28(H28), C38(H38A,H38B,H38C),
 O19(H19), O18(H18A), O16(H16), O20(H20A), C37(H37A,H37B,H37C), O17(H17),
 O21(H21), O2W(H2WA,H2WB)
5.b Aromatic/amide H refined with riding coordinates:
 N2(H2), N6(H6), C3(H3), C5(H5), C7(H7), C9(H9), C13(H13), C13X(H13X),
 C11(H11), C11(H11A), C18(H18), C20(H20), C22(H22), C24(H24), C26X(H26X),
 C28X(H28X)
5.c Fitted hexagon refined as free rotating group:
 C13X(C12X,C11,C10,C15X,C14X), C27X(C26X,C25,C30,C29X,C28X)
5.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C40(H40B,H40C,H40A), C35(H35A,H35B,
 H35C), C36(H36A,H36C,H36B), C39(H39A,H39B,H39C), C34(H34A,H34B,H34C)
;
_olex2_submission_special_instructions 'No special instructions were received'