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_7229727
_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 Ti, 2(C7 H15 N2), I'
_chemical_formula_sum            'C46 H46 I N12 O Ti'
_chemical_formula_weight         957.75
_chemical_melting_point          ?
_chemical_name_common            no
_chemical_name_systematic
'salt of titanyl phthalocyanine with two N-methyldiazabicyclooctanium cations and iodine anion'
_chemical_properties_physical    Air-sensitive,Oxygen-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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_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                 91.733(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5787(7)
_cell_length_b                   13.0731(5)
_cell_length_c                   25.4452(17)
_cell_measurement_reflns_used    18294
_cell_measurement_temperature    130.00(14)
_cell_measurement_theta_max      29.0490
_cell_measurement_theta_min      1.6320
_cell_volume                     4182.4(4)
_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)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      130.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.895
_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    -37.00  29.00   1.00   50.00    --  -12.20  37.00  60.00   66
  2  \w    -33.00  -7.00   1.00   50.00    --  -12.20 -37.00 -90.00   26
  3  \w    -61.00  12.00   1.00   50.00    --  -12.20 -37.00  30.00   73
  4  \w    -14.00  13.00   1.00   50.00    --  -12.20 -57.00 -30.00   27
  5  \w     -3.00  23.00   1.00   50.00    --   11.89 -37.00-150.00   26
  6  \w    -27.00  -1.00   1.00   50.00    --  -12.20 -57.00   0.00   26
  7  \w     35.00  69.00   1.00   50.00    --  -12.20  19.00 -30.00   34
  8  \w    -40.00  10.00   1.00   50.00    --  -12.20 -57.00 120.00   50
  9  \w    -80.00 -54.00   1.00   50.00    --  -12.20 -37.00-150.00   26
 10  \w     34.00  61.00   1.00   50.00    --  -12.20  19.00 120.00   27
 11  \w    -85.00   9.00   1.00   50.00    --  -12.20 -57.00-120.00   94
;
_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      -0.0290920000
_diffrn_orient_matrix_UB_12      0.0024691000
_diffrn_orient_matrix_UB_13      -0.0243004000
_diffrn_orient_matrix_UB_21      0.0467852000
_diffrn_orient_matrix_UB_22      -0.0121765000
_diffrn_orient_matrix_UB_23      -0.0135124000
_diffrn_orient_matrix_UB_31      -0.0121176000
_diffrn_orient_matrix_UB_32      -0.0528522000
_diffrn_orient_matrix_UB_33      0.0019681000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.895
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            50066
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.624
_diffrn_reflns_theta_min         1.601
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.996
_exptl_absorpt_correction_T_max  0.912
_exptl_absorpt_correction_T_min  0.809
_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    1.521
_exptl_crystal_description       block
_exptl_crystal_F_000             1956
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane/dichlorobenzene'
_exptl_crystal_size_max          0.208
_exptl_crystal_size_mid          0.204
_exptl_crystal_size_min          0.085
_refine_diff_density_max         1.332
_refine_diff_density_min         -0.903
_refine_diff_density_rms         0.092
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     552
_refine_ls_number_reflns         10563
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0664
_refine_ls_R_factor_gt           0.0485
_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^)+(0.0287P)^2^+7.5995P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0943
_refine_ls_wR_factor_ref         0.1006
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8487
_reflns_number_total             10563
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ce01918a2.cif
_cod_data_source_block           TIOPc2MDABCOI
_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               7229727
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C209 H190 N19 Ti19 O19 I1'
_reflns_odcompleteness_completeness 99.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C301(H30A,H30B), C302(H30C,H30D), C303(H30E,H30F), C304(H30G,H30H), C305(H30I,
 H30J), C306(H30K,H30L), C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F),
 C204(H20G,H20H), C205(H20I,H20J), C206(H20K,H20L)
2.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)
2.c Idealised Me refined as rotating group:
 C307(H30M,H30N,H30O), C207(H20M,H20N,H20O)
;
_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 1.136
_oxdiff_exptl_absorpt_empirical_full_min 0.871