Salts with titanyl and vanadyl phthalocyanine radical anions. Molecular design and effect of cations on the structure and magnetic and optical properties
Konarev, Dmitri V.; Kuzmin, Alexey V.; Khasanov, Salavat S.; Batov, Mikhail S.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N.; CrystEngComm 20 (2018) 385–; doi:10.1039/C7CE01918A

data_7229724
_publ_section_title
;
 Salts with titanyl and vanadyl phthalocyanine radical anions. Molecular
 design and effect of cations on the structure and magnetic and optical
 properties
;
_journal_issue                   4
_journal_name_full               CrystEngComm
_journal_page_first              385
_journal_paper_doi               10.1039/C7CE01918A
_journal_volume                  20
_journal_year                    2018
_chemical_compound_source        no
_chemical_formula_moiety         'C32 H16 N8 O V, C24 H52 N, C6 H4 Cl2'
_chemical_formula_sum            'C62 H72 Cl2 N9 O V'
_chemical_formula_weight         1081.12
_chemical_melting_point          ?
_chemical_name_common            no
_chemical_name_systematic
'salt of vanadyl phthalocyanine with tetrahexylammonium cation, o-dichlobenzene solvate'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-03-23
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2017.03.22 svn.r3403 for OlexSys, GUI svn.r5332)
;
_audit_update_record
;
2017-10-23 deposited with the CCDC.
2017-12-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.783(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.9200(6)
_cell_length_b                   11.7027(3)
_cell_length_c                   21.2051(6)
_cell_measurement_reflns_used    9240
_cell_measurement_temperature    109.95(10)
_cell_measurement_theta_max      30.4550
_cell_measurement_theta_min      1.9430
_cell_volume                     5658.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      109.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.887
_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    -44.00 -17.00   1.00  100.00    --   15.86 -19.00-120.00   27
  2  \w    -13.00  38.00   1.00  100.00    --   15.86 -57.00  30.00   51
  3  \w    -48.00  38.00   1.00  100.00    --   15.86 -57.00 120.00   86
  4  \w    -45.00 -19.00   1.00  100.00    --  -16.01 -37.00 -60.00   26
  5  \w    -74.00  14.00   1.00  100.00    --  -16.01 -57.00-120.00   88
  6  \w    -84.00 -50.00   1.00  100.00    --  -16.01 -59.00 176.32   34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0089578000
_diffrn_orient_matrix_UB_12      -0.0555962000
_diffrn_orient_matrix_UB_13      -0.0082265000
_diffrn_orient_matrix_UB_21      0.0081487000
_diffrn_orient_matrix_UB_22      0.0213253000
_diffrn_orient_matrix_UB_23      -0.0291812000
_diffrn_orient_matrix_UB_31      0.0286652000
_diffrn_orient_matrix_UB_32      0.0113271000
_diffrn_orient_matrix_UB_33      0.0145524000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0249
_diffrn_reflns_av_unetI/netI     0.0473
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.887
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            22958
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.887
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         31.027
_diffrn_reflns_theta_min         1.956
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.320
_exptl_absorpt_correction_T_max  0.895
_exptl_absorpt_correction_T_min  0.803
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.269
_exptl_crystal_description       trapezoid
_exptl_crystal_F_000             2288
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane-o-dichlorobenzene'
_exptl_crystal_size_max          0.283
_exptl_crystal_size_mid          0.189
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.492
_refine_diff_density_min         -0.516
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.367(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     692
_refine_ls_number_reflns         12469
_refine_ls_number_restraints     206
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0406
_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^)+(0.0395P)^2^+2.1419P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0835
_refine_ls_wR_factor_ref         0.0898
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.887
_reflns_number_gt                10847
_reflns_number_total             12469
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ce01918a2.cif
_cod_data_source_block           VOPcHexyl4NC6H4Cl2
_cod_depositor_comments
;
The following automatic conversions were performed:

'_chemical_melting_point' value 'not measured' was changed to '?' -
the value is undefined or not given.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

 Adding full bibliography for 7229722--7229730.cif.
;
_cod_database_code               7229724
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C248 H288 Cl8 N36 O4 V4'
_reflns_odcompleteness_completeness 99.38
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.633(18)
 0.367(18)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A: within 1.7A with sigma
of 0.004 and sigma for terminal atoms of 0.008
C22A \\sim C24A \\sim C203 \\sim C24B: within 1.7A with sigma of 0.004 and
sigma for terminal atoms of 0.008
C106 \\sim C107 \\sim C121 \\sim C122 \\sim C123 \\sim C124: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008
C102 \\sim C103 \\sim C117 \\sim C118 \\sim C119 \\sim C120: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008
C110 \\sim C111 \\sim C125 \\sim C126 \\sim C127 \\sim C128: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008
C114 \\sim C115 \\sim C129 \\sim C130 \\sim C131 \\sim C132: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C24B) = Uanis(C24A)
Uanis(C25B) = Uanis(C25A)
Uanis(C26B) = Uanis(C26A)
4. Others
 Sof(H20K)=Sof(H20L)=Sof(C24B)=Sof(H24C)=Sof(H24D)=Sof(C25B)=Sof(H25C)=
 Sof(H25D)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(1)
 Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(C25A)=Sof(H25A)=Sof(H25B)=Sof(C26A)=
 Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(H20I)=Sof(H20J)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C201(H20A,H20B), C207(H20C,H20D), C208(H20E,H20F), C209(H20G,H20H), C210(H21A,
 H21B), C211(H21C,H21D), C213(H21H,H21I), C214(H21J,H21K), C215(H21L,H21M),
 C216(H21N,H21O), C217(H21P,H21Q), C219(H21U,H21V), C220(H22A,H22B), C221(H22C,
 H22D), C222(H22E,H22F), C223(H22G,H22H), C22A(H22L,H22M), C24A(H24A,H24B),
 C25A(H25A,H25B), C203(H20I,H20J), C203(H20K,H20L), C24B(H24C,H24D), C25B(H25C,
 H25D)
5.b Aromatic/amide H refined with riding coordinates:
 C117(H117), C118(H118), C119(H119), C120(H120), C121(H121), C122(H122),
 C123(H123), C124(H124), C125(H125), C126(H126), C127(H127), C128(H128),
 C129(H129), C130(H130), C131(H131), C132(H132), C3A(H3A), C4A(H4A), C5A(H5A),
 C6A(H6A)
5.c Idealised Me refined as rotating group:
 C212(H21E,H21F,H21G), C218(H21R,H21S,H21T), C224(H22I,H22J,H22K), C26A(H26A,
 H26B,H26C), C26B(H26D,H26E,H26F)
;
_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 1.134
_oxdiff_exptl_absorpt_empirical_full_min 0.915